WO1996036664A1 - Composition for producing solid materials, particularly sanitary ware - Google Patents

Composition for producing solid materials, particularly sanitary ware Download PDF

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Publication number
WO1996036664A1
WO1996036664A1 PCT/FR1996/000752 FR9600752W WO9636664A1 WO 1996036664 A1 WO1996036664 A1 WO 1996036664A1 FR 9600752 W FR9600752 W FR 9600752W WO 9636664 A1 WO9636664 A1 WO 9636664A1
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WIPO (PCT)
Prior art keywords
filler
composition
resin
weight
composition according
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PCT/FR1996/000752
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French (fr)
Inventor
Jérôme ROBERTY
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Nayad Diffusion
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Publication of WO1996036664A1 publication Critical patent/WO1996036664A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the invention relates to a composition intended for the manufacture of solid materials, in particular the manufacture of materials used in the manufacture of sanitary objects such as baths.
  • the composition comprises a polymeric casting resin as well as an inert filler comprising a porous filling filler of medium density, in particular consisting of two porous fillers of different mean particle size diameters, as well as an insulating filler consisting of hollow glass microspheres in proportion by weight substantially less than the proportion by weight of the filling charge.
  • metasphere type filler
  • porous filling fillers of average density and of variable mean particle size diameter, in particular of the calcium carbonate type, and in particular of two fillers of different average particle size diameters, coupled with the use of a small percentage of glass microspheres makes it possible to obtain a material which not only has a smooth surface but also exhibits significant thermal and sound insulation characteristics, such characteristics being particularly desirable in applications such as the manufacture of baths.
  • Glass microspheres represent a particularly advantageous additional filler in the context of the present invention when they are used in very small quantities. Indeed, their low density as well as the volume of air which they contain make it possible to improve the insulating properties of the material obtained.
  • the inventors had considered completely eliminating the glass microspheres and increasing the amount of calcium carbonate in the composition by using calcium carbonate having a very small mean particle size diameter (similar to that of glass microspheres) coupled with calcium carbonate fillers with larger average particle size diameters. This alternative has proven to be disadvantageous on several levels.
  • the calcium carbonate of very small particle size diameter has a very high density which considerably increases the mass of the composition without giving it advantageous thermal insulation properties.
  • the present invention therefore relates to a composition intended for the manufacture of a solid material, in particular of materials used in the sanitary field.
  • This composition is characterized in that it comprises:
  • a polymeric casting resin having characteristics of wettability of load, mechanical resistance, low heating during its polymerization and absence of deformation under heat once solidified;
  • an inert filler which does not react with the substances used in the composition of the polymeric resin, said inert filler being characterized in that it comprises:
  • a porous filling filler of medium density in particular of the calcium carbonate type, having a variable particle size diameter, in particular consisting of two charges of different average particle size diameters, in particular greater than approximately 1 ⁇ m and less than approximately 500 ⁇ m;
  • the porous filling charge consists in particular of two charges of calcium carbonate or of a substance having similar properties having respective mean particle size diameters varying between 1 and 300 ⁇ m and between 1 and 500 ⁇ m, in particular respective mean particle size diameters varying between 1 and 100 ⁇ m and 100 and 500 ⁇ m.
  • the respective weight percentages of these two fillers normally vary between 8 and 20% by weight, particularly between 10 to 15% by weight for a calcium carbonate of average diameter varying between 1 and 300 ⁇ m and from 20 to 35% by weight, particularly from 25 to 30% by weight for a calcium carbonate of average diameter varying between 100 and 500 ⁇ m.
  • the composition according to the invention comprises between 1 and 10%, in particular between 1 and 4% by weight of hollow glass microspheres having a diameter varying between 5 and 200 ⁇ m, in particular between 10 and 100 ⁇ m.
  • the present invention also relates to a composite material comprising the composition described above as well as a solid reinforcement support covering the external surface of this composition.
  • the solid support comprises a layer of laminated glass fiber impregnated with a polymeric resin, the laminated glass fiber (including the resin) having a surface mass varying from 1000 to 1500 g / m 3 , and in particular from 1200 g / m 3 .
  • the inventors have therefore discovered that the use of a small amount of glass microspheres coupled with a charge of porous filling with a variable particle size diameter makes it possible to effectively seal the interstices between the various granulations of the calcium carbonate particles and thus to obtain a solid material with a smooth surface having mechanical resistance as well as thermal insulation properties and considerable phonic.
  • inert fillers comprising either only porous filling fillers of the calcium carbonate type, or high amounts of microspheres or either a porous filling filler comprising a very variable particle size diameter.
  • These compositions have either too high a density, or a low mechanical resistance, or a high cost, or an undesirable porous structure.
  • the invention relates to a composition intended for the manufacture of a solid material comprising a polymeric resin of the orthophthalic polyester resin type as well as an inert filler comprising a porous filler of medium density and of variable particle size diameter preferably comprising two fillers.
  • This composition when used in the sanitary field, offers mechanical strength and significant thermal and phonic insulation properties obtained thanks to its high density, obtained without increase in weight, by the selection of the nature as well as the particle size of its components and by the addition of air charges located inside the glass microspheres and which conserve the heat of the water.
  • the main applications of the composition of the invention are in the sanitary field, its use is also envisaged in the building field, in the manufacture of tables or furniture.
  • the fields of application extend to the manufacture of any type of material requiring a dense and smooth surface condition.
  • the choice of the type and the proportion of its main components, namely the casting resin, the filling filler as well as the insulating filler must be made with care.
  • the type of resin that can be used in the compositions of the invention is very variable and its choice can easily be made by the person skilled in the art who would take into account a certain number of selection criteria.
  • the resin used in the composition of the invention should ideally have good filler wettability, as well as good mechanical strength.
  • the polymeric resin should be characterized by an absence of heating during its polymerization, this having the aim of avoiding affecting the molds used in the manufacture of the solid material.
  • the polymeric resin used should not deform under heat substantially.
  • the casting resin used in the composition of the present invention is an unsaturated polyester and / or vinylester resin. Such resins have the advantage of having short drying times as well as excellent adhesive properties.
  • the casting resin is an orthophthalic polyester resin of the sterpon 3780-15 type sold by the company CONVERT.
  • the proportion of resin used in the composition of the invention can vary between 20 and 60% by weight, in particular between 50 and 60% by weight. Although it is desirable to use as little resin as possible, a percentage varying between 50 and 60% is preferable in order to be able to obtain the desired rigidity and adhesion.
  • the filling filler is a porous filler capable of absorbing a certain quantity of resin in the liquid state and having a medium density.
  • They are generally inorganic fillers of the calcium carbonate or clay type. Fillers of the calcium carbonate type are preferred because of their low cost and the possibility of easily obtaining a large number of different particle sizes.
  • One of the preferred embodiments of the invention provides for the use of two filling charges of different mean particle size diameters, lying between 1 and 500 ⁇ m. Large amounts of fillers with an average diameter of less than 100 are not desirable. The percentage by weight of the filling filler being relatively high, the very small particle size diameters give compositions with too high a density therefore too heavy.
  • the filling charge is ideally made up of approximately 13 to 14% by weight of calcium carbonate of average diameter varying between 1 and 200 ⁇ m and approximately 26 to 27% of calcium carbonate of diameter varying between 100 and 500 ⁇ m.
  • Typical examples of calcium carbonate used in the context of the present invention include carbonates of calcium sold by the company OMYA under the brands Durcal 30, Durcal 40 and Durcal 130.
  • a minimum quantity of filler of the order of approximately 30% is necessary in order to be able to obtain a composition having the desired properties. This minimum quantity can hardly be replaced either by glass microspheres or by an additional quantity of resin. A high amount of glass microspheres considerably increases the cost of the composition.
  • the use of large quantities causes problems with the heating of the molds and more importantly, the quick-curing resins tend to crack during drying.
  • the use of a minimum quantity of fillers allows these fillers to act as a polymerization damper and thus avoid the problems of heating and cracking of the resin.
  • the use of a filling filler makes it possible to reduce the shrinking effect observed during the drying of the resin, b) insulating filler
  • the insulating filler consists of hollow glass microspheres whose proportion by weight varies between 1 and 10%, in particular between 1 and 4%. Although the proportion of hollow glass microspheres present in the composition of the invention is quite low, this proportion has been found to be sufficient to confer increased thermal and sound insulation properties on the material of the invention when compared to a material of the same type not comprising microspheres. The thermal insulation properties are of course particularly desirable in the sanitary field.
  • hollow glass microspheres coupled with an adequate filling load allows the manufacture of a material having a mechanical strength sufficiently high to be able to use it in certain applications without it being covered with a support.
  • solid reinforcement such as a glass fiber support impregnated with polymeric resin, This would not have been possible with the materials described in the prior art.
  • This phenomenon therefore results from the combination of a percentage by weight of at least 40% of a filling filler of variable mean particle size diameter of at least 40%, in particular of charging with a small percentage of insulating filler consisting of microspheres of hollow glass.
  • microspheres having a low nominal density of the order of 0.1 to 0.3 g / cm 3 , will preferably be chosen.
  • the low density microspheres are chosen because of their low weight and their large volume which favors the addition of a higher air charge, thus increasing the heat conservation properties of the material obtained.
  • the microspheres sold under the reference K1, K15, K20 or K25 by the company 3M are in particular used in proportion by weight varying from 1 to 10% but more particularly in proportion by weight varying from 1 to 4%. Additional components
  • composition of the invention may also comprise a catalyst for the polymerization of the casting resin.
  • a catalyst for the polymerization of the casting resin The choice of the appropriate catalyst is part of the knowledge of a person skilled in the art.
  • catalysts of the methyl ethyl ketone peroxide type such as the catalysts sold by the company AKZO under the brand Butanox and more particularly under the brand Butanox M-50 can be used.
  • accelerators that promote the curing of unsaturated polyester resins at room temperature.
  • Cobalt octanoate accelerators also sold by AKZO under the brands Accelerator NL51 P or Accelerator NL51 S, are the accelerators of choice.
  • the present invention also relates to a composite material comprising the composition described above as well as a solid reinforcement support covering the exterior surface.
  • a solid reinforcement support may prove essential in certain applications. Indeed, the composition of the invention remains first and foremost a flowable substance. Although the inventors have demonstrated that it is possible to use it without reinforcing support in certain applications, which previously proved impossible, both in terms of the low mechanical resistance of the compositions of the prior art and of absence of a non-porous exterior surface, better yields are obtained when a solid reinforcement support is applied to the exterior surface.
  • One of the materials of choice used as a reinforcing support comprises a layer of laminated glass fibers impregnated with a polymeric resin.
  • the laminated glass fibers can take the form of felt glass fibers cut and agglomerated by a liquid binder with high solubility in styrene.
  • the fiberglass must be flexible, have great ease of handling and be able to be impregnated with polyester resin without difficulty.
  • An example of the type of glass fiber which can be used in the context of the present invention is Mat M4 sold by the company VETROTEX.
  • the surface mass of the laminated glass fiber support generally varies between 1000 and 1500 g / m 2 .
  • the fiber of laminated glass has a basis weight of approximately 1200 g / m 2 .
  • the thickness of the layer of laminated glass fibers may be varied according to the desired applications.
  • the thickness of the layer of glass fibers varies between 0.5 and 1.5 mm.
  • the thickness of the layer of laminated glass fibers is approximately 1 MM.
  • compositions of the invention the use of solid reinforcements in addition to or in replacement of glass fibers is also envisaged.
  • solidifying substances of the Gelcoat type making it possible to obtain a flexible, hard and shiny surface film successfully supporting aging tests, can be used.
  • this type of substance examples include formulas based on isophthalic acid and neoantylglycol such as the Gelcoat Sterpon 40 sold by the company CONVERT.
  • the thickness of this type of coating normally varies between 0.4 mm and 0.6 mm and preferably is around 0.5 mm.
  • the production timeline for the composition of the present invention corresponds to the timeline currently used by the person skilled in the art for the manufacture of compositions of the same type. This chronology will only be slightly modified according to the use or not of a solid reinforcement support.
  • the resin is first mixed with the accelerator.
  • the inert filler is then incorporated into the mixture.
  • it is not absolutely necessary to stick to a precise order it is preferable to incorporate first the porous filler of smaller particle size diameter, followed by the porous filler of smaller particle size diameter high to finish with the incorporation of the insulating filler made up of hollow glass microspheres.
  • the catalyst is then incorporated and the composition is then mixed until a homogeneous substance is obtained.
  • the mixture is then poured by gravity between a mold and a counter-mold. The casting is followed by a more or less long drying period which will depend on the catalyst used.
  • the various elements of the casting for a period varying between 10 and 30 min and preferably for a period of about 25 min to obtain a homogeneous mixture.
  • the casting should normally take place between 5 and 10 min after the incorporation of the catalyst into the casting, although this period may also be varied depending on the catalyst used.
  • the drying time required to observe sufficient solidification of the mixture generally varies between 30 and 90 min.
  • composition of the present invention When the composition of the present invention is covered with a solid reinforcing support consisting of glass fibers, the latter are applied to the molds before casting. The casting is only introduced into the molds after the glass fiber support has dried.
  • 240 g of orthophthalic resin of the Convert brand are mixed with 240 g of porous filler with a small particle size diameter sold by the company OMYA under the reference Durcal 40 and 460 g of porous filler with diameter high marketed by the company OMYA under the Durcal reference 130 and 35 g of charge of hollow glass microspheres of type K1 marketed by the company 3M.
  • the casting is carried out in a suitable mold at room temperature and the composition thus obtained is dried for a period of approximately 12 hours to avoid any deformation before being demolded.
  • the manufacture of such a material is carried out in three stages. It is firstly a question of applying approximately 0.5 mm of a sanitary gelcoat of isophthalic quality such as the Gelcoat Sterpon 4040 marketed by the company CONVERT SA. Once the Gelcoat has dried, a glass mat having a surface mass of 300 g / m 2 and impregnated with an isophthalic polyester resin is applied to the surface of the mold, using a contact molding method. The thickness of this second coating is approximately 1 mm.
  • Example 1 After this layer of laminated glass fibers has dried, the two parts of the mold are assembled and the casting resin produced in Example 1 is poured by gravity between the mold and the counter-mold. The whole is then dried and then removed from the mold.

Abstract

A composition for producing a solid material is described, particularly materials used for producing sanitary ware, characterised in that it contains a casting polymeric resin and an inert filler which does not react with the substances composing said polymeric resin. The filler comprises a porous filler material, particularly made up of two fillers of different average particle diameters, and one insulating filler made of hollow glass microspheres, in a weight content substantially lower than the weight content of the porous filler material. The amount and type of porous filler material, and the amount of hollow microspheres present in said material are sufficient to provide the material with a smooth and dense surface state and mechanical strength, as well as enhanced heat and sound insulation properties, compared to similar materials containing a single filler material and/or not containing microspheres.

Description

COMPOSITION DESTINE A LA FABRICATION DE MATERIAUX SOLIDES,NOTAMMENT D'OBJECTS SANITAIRECOMPOSITION FOR THE MANUFACTURE OF SOLID MATERIALS, ESPECIALLY SANITARY OBJECTS
L'invention concerne une composition destinée à la fabrication de matériaux solides, notamment la fabrication de matériaux utilisés dans la fabrication d'objets sanitaires telles les baignoires. La composition comprend une résine polymérique de coulée ainsi qu'une charge inerte comprenant une charge de remplissage poreuse de densité moyenne, notamment constituée de deux charges poreuses de diamètres granulométriques moyens différents, ainsi qu'une charge isolante constituée de microsphères de verre creuses en proportion en poids substantiellement inférieure à la proportion en poids de la charge de remplissage.The invention relates to a composition intended for the manufacture of solid materials, in particular the manufacture of materials used in the manufacture of sanitary objects such as baths. The composition comprises a polymeric casting resin as well as an inert filler comprising a porous filling filler of medium density, in particular consisting of two porous fillers of different mean particle size diameters, as well as an insulating filler consisting of hollow glass microspheres in proportion by weight substantially less than the proportion by weight of the filling charge.
Depuis plusieurs années, des résines polymériques de coulée sont utilisées avec des charges de remplissage quelconques pour fabriquer des matériaux susceptibles d'être utilisés dans le bâtiment, et plus particulièrement pour des applications sanitaires telles la fabrication de baignoires. Toutefois, un certain nombre de problèmes ont été notés concernant la quantité de résine ainsi que le type et la quantité de charge utilisés, sachant qu'il est souhaitable d'obtenir un matériau possédant une bonne résistance mécanique.For several years, polymeric casting resins have been used with any fillers to manufacture materials capable of being used in the building industry, and more particularly for sanitary applications such as the manufacture of baths. However, a number of problems have been noted regarding the amount of resin as well as the type and amount of filler used, knowing that it is desirable to obtain a material having good mechanical strength.
On a suggéré l'utilisation de quantités considérables de charge de type « métasphères » dans des compositions comprenant des résines polymériques de coulée. Ces métasphères sont fabriquées à partir de substances polymériques et présentent donc une densité assez faible.It has been suggested that considerable amounts of "metasphere" type filler be used in compositions comprising polymeric casting resins. These metaspheres are made from polymeric substances and therefore have a fairly low density.
L'inconvénient majeur noté lors de l'utilisation de telles substances était qu'elles réagissaient assez facilement avec la résine de coulée. Ceci entraînait des modifications de structure indésirables et altérait ultimement les propriétés de la composition. Plusieurs documents d'art antérieur ont également suggéré l'utilisation de microsphères de verre dans des compositions comprenant des résines polymériques. A titre d'exemples, on peut citer la demande de brevet européen 0547593 publiée le 23 juin 1993, la demande de brevet européen 0626433 publiée le 30 novembre 1994 décrivant un apprêt liquide, la demande de brevet britannique GB 2114466 ainsi que la demande de brevet australien 9226170 qui décrit la fabrication d'articles renforcés comprenant des feuilles d'acrylique. Dans la plupart de ces documents, on suggère l'utilisation de quantités considérables de microsphères de verre. Des quantités élevées de microsphères ont le désavantage de fragiliser la structure du matériau en diminuant sa résistance mécanique.The major drawback noted when using such substances was that they reacted fairly easily with the casting resin. This resulted in undesirable structural changes and ultimately altered the properties of the composition. Several prior art documents have also suggested the use of glass microspheres in compositions comprising polymeric resins. As examples, we can cite the European patent application 0547593 published on June 23, 1993, the patent application European 0626433 published on November 30, 1994 describing a liquid finish, the British patent application GB 2114466 as well as the Australian patent application 9226170 which describes the manufacture of reinforced articles comprising acrylic sheets. Most of these documents suggest the use of considerable amounts of glass microspheres. High amounts of microspheres have the disadvantage of weakening the structure of the material by reducing its mechanical strength.
Les inventeurs ont découvert que l'utilisation de charges de remplissage poreuses de densité moyenne, et de diamètre granulométrique moyen variable, notamment de type carbonate de calcium, et en particulier de deux charges de diamètres granulométriques moyens différents, couplées à l'utilisation d'un faible pourcentage de microsphères de verre permet d'obtenir un matériau ayant non seulement une surface lisse mais présentant également des caractéristiques d'isolation thermique et phonique importantes, de telles caractéristiques étant particulièrement souhaitables dans des applications telles que la fabrication de baignoires.The inventors have discovered that the use of porous filling fillers of average density and of variable mean particle size diameter, in particular of the calcium carbonate type, and in particular of two fillers of different average particle size diameters, coupled with the use of a small percentage of glass microspheres makes it possible to obtain a material which not only has a smooth surface but also exhibits significant thermal and sound insulation characteristics, such characteristics being particularly desirable in applications such as the manufacture of baths.
Des matériaux présentant des surfaces lisses, sans interstices, sont particulièrement souhaitables pour des applications sanitaires. A cet égard, l'utilisation combinée d'une charge de remplissage poreuse de diamètre moyen unique de type carbonate de calcium et de microsphères de verre ne permettait pas d'obtenir un matériau possédant les propriétés désirées. On obtenait plutôt un matériau assez poreux, la présence d'interstices n'étant pas souhaitable. Les inventeurs ont obtenu des matériaux résistants possédant des surfaces lisses en utilisant une charge de remplissage poreuse possédant un diamètre granulométique variable, notamment deux charges de diamètres moyens différents.Materials with smooth surfaces, without gaps, are particularly desirable for sanitary applications. In this regard, the combined use of a porous filler with a single average diameter of the calcium carbonate type and glass microspheres did not make it possible to obtain a material having the desired properties. Rather, a fairly porous material was obtained, the presence of interstices being undesirable. The inventors have obtained resistant materials having smooth surfaces by using a porous filling filler having a variable particle size diameter, in particular two fillers of different average diameters.
Les microsphères de verre représentent une charge complémentaire particulièrement intéressante dans le cadre de la présente invention lorsqu'elles sont utilisées en quantités très faibles. En effet, leur faible masse volumique ainsi que le volume d'air qu'elles contiennent permettent d'améliorer les propriétés isolantes du matériau obtenu. Les inventeurs avaient envisagé d'éliminer complètement les microsphères de verre et d'augmenter la quantité de carbonate de calcium dans la composition en utilisant du carbonate de calcium possédant un très faible diamètre granulométrique moyen (semblable à celui des microsphères de verre) couplé à des charges de carbonate de calcium possédant des diamètres granulométiques moyens plus élevés. Cette alternative s'est avérée désavantageuse à plusieurs niveaux. Entre autres, le carbonate de calcium de très faible diamètre granulométrique possède une densité très élevée qui augmente considérablement la masse de la composition sans pour autant lui conférer des propriétés d'isolation thermique intéressantes.Glass microspheres represent a particularly advantageous additional filler in the context of the present invention when they are used in very small quantities. Indeed, their low density as well as the volume of air which they contain make it possible to improve the insulating properties of the material obtained. The inventors had considered completely eliminating the glass microspheres and increasing the amount of calcium carbonate in the composition by using calcium carbonate having a very small mean particle size diameter (similar to that of glass microspheres) coupled with calcium carbonate fillers with larger average particle size diameters. This alternative has proven to be disadvantageous on several levels. Among other things, the calcium carbonate of very small particle size diameter has a very high density which considerably increases the mass of the composition without giving it advantageous thermal insulation properties.
La présente invention concerne donc une composition destinée à la fabrication d'un matériau solide, notamment de matériaux utilisés dans le domaine sanitaire. Cette composition est caractérisée en ce qu'elle comprend :The present invention therefore relates to a composition intended for the manufacture of a solid material, in particular of materials used in the sanitary field. This composition is characterized in that it comprises:
- une résine polymérique de coulée présentant des caractéristiques de mouillabilité de charge, de résistance mécanique, de faible chauffage lors de sa polymérisation et d'absence de déformation sous la chaleur une fois solidifiée ; et- A polymeric casting resin having characteristics of wettability of load, mechanical resistance, low heating during its polymerization and absence of deformation under heat once solidified; and
- une charge inerte ne réagissant pas avec les substances entrant dans la composition de la résine polymérique, ladite charge inerte étant caractérisée en ce qu'elle comprend :an inert filler which does not react with the substances used in the composition of the polymeric resin, said inert filler being characterized in that it comprises:
- une charge de remplissage poreuse de densité moyenne, notamment de type carbonate de calcium, possédant un diamètre granulométrique variable, notamment constituée de deux charges de diamètres granulométriques moyens différents, notamment supérieurs à environ 1 μm et inférieurs à environ 500 μm ; eta porous filling filler of medium density, in particular of the calcium carbonate type, having a variable particle size diameter, in particular consisting of two charges of different average particle size diameters, in particular greater than approximately 1 μm and less than approximately 500 μm; and
- une charge isolante constituée de microsphères de verre creuses en proportion en poids substantiellement inférieure à la proportion en poids de la charge de remplissage présente dans le matériau, la quantité ainsi que le type de charge de remplissage poreuse ainsi que la quantité de microsphères de verre creuses présentes dans le matériau étaient suffisantes pour conférer au matériau un état de surface lisse et dense et une résistance mécanique ainsi que des caractéristiques d'isolations thermique et phonique accrues lorsque comparées à un matériau de même type comprenant une charge de remplissage de diamètre moyen unique et/ou ne comprenant pas de microsphères.an insulating filler made up of hollow glass microspheres in proportion by weight substantially lower than the proportion by weight of the filling filler present in the material, quantity as well as the type of porous filling charge as well as the quantity of hollow glass microspheres present in the material were sufficient to give the material a smooth and dense surface condition and a mechanical resistance as well as thermal and sound insulation characteristics increased when compared to a material of the same type comprising a filler with a single average diameter and / or not comprising microspheres.
La charge de remplissage poreuse est notamment constituée de deux charges de carbonate de calcium ou d'une substance possédant des propriétés semblables présentant des diamètres granulométriques moyens respectifs variant entre 1 et 300 μm et entre 1 et 500 μm, notamment de diamètres granulométriques moyens respectifs variant entre 1 et 100 μm et 100 et 500 μm. Les pourcentages en poids respectifs de ces deux charges varie normalement entre 8 et 20% en poids, particulièrement entre 10 à 15% en poids pour un carbonate de calcium de diamètre moyen variant entre 1 et 300 μm et de 20 à 35% en poids, particulièrement de 25 à 30% en poids pour un carbonate de calcium de diamètre moyen variant entre 100 et 500 μm.The porous filling charge consists in particular of two charges of calcium carbonate or of a substance having similar properties having respective mean particle size diameters varying between 1 and 300 μm and between 1 and 500 μm, in particular respective mean particle size diameters varying between 1 and 100 μm and 100 and 500 μm. The respective weight percentages of these two fillers normally vary between 8 and 20% by weight, particularly between 10 to 15% by weight for a calcium carbonate of average diameter varying between 1 and 300 μm and from 20 to 35% by weight, particularly from 25 to 30% by weight for a calcium carbonate of average diameter varying between 100 and 500 μm.
De façon préférentielle, la composition selon l'invention comprend entre 1 et 10%, notamment entre 1 et 4% en poids de microsphères de verre creuses ayant un diamètre variant entre 5 et 200 μm, notamment entre 10 et 100 μm.Preferably, the composition according to the invention comprises between 1 and 10%, in particular between 1 and 4% by weight of hollow glass microspheres having a diameter varying between 5 and 200 μm, in particular between 10 and 100 μm.
La présente invention est également relative à un matériau composite comprenant la composition décrite précédemment ainsi qu'un support de renfort solide recouvrant la surface extérieure de cette composition. De façon préférée, le support solide comprend une couche de fibre de verre stratifiée imprégnée d'une résine polymérique, la fibre de verre stratifiée (incluant la résine) possédant une masse surfacique variant de 1000 à 1500 g/m3, et notamment de 1200 g/m3. Les inventeurs ont donc découvert que l'utilisation d'une faible quantité de microsphères de verre couplée à une charge de remplissage poreuse possédant un diamètre granulométrique variable permet d'assurer un colmatage efficace des interstices entre les diverses granulations des particules de carbonate de calcium et d'obtenir ainsi un matériau solide de surface lisse présentant une résistance mécanique ainsi que des propriétés d'isolations thermique et phonique considérables.The present invention also relates to a composite material comprising the composition described above as well as a solid reinforcement support covering the external surface of this composition. Preferably, the solid support comprises a layer of laminated glass fiber impregnated with a polymeric resin, the laminated glass fiber (including the resin) having a surface mass varying from 1000 to 1500 g / m 3 , and in particular from 1200 g / m 3 . The inventors have therefore discovered that the use of a small amount of glass microspheres coupled with a charge of porous filling with a variable particle size diameter makes it possible to effectively seal the interstices between the various granulations of the calcium carbonate particles and thus to obtain a solid material with a smooth surface having mechanical resistance as well as thermal insulation properties and considerable phonic.
Ceci constitue un avantage par rapport à l'utilisation de charges inertes comprenant soit uniquement des charges de remplissage poreuses de type carbonate de calcium, soit des quantités élevées de microsphères ou soit une charge de remplissage poreuse comprenant un diamètre granulométrique peu variable. Ces compositions présentent soit une densité trop élevée, soit une faible résistance mécanique, soit un coût élevé, soit une structure poreuse non désirable.This constitutes an advantage compared to the use of inert fillers comprising either only porous filling fillers of the calcium carbonate type, or high amounts of microspheres or either a porous filling filler comprising a very variable particle size diameter. These compositions have either too high a density, or a low mechanical resistance, or a high cost, or an undesirable porous structure.
L'invention sera décrite davantage en se référant à la description qui suit. Description détaillée de l'inventionThe invention will be further described with reference to the following description. Detailed description of the invention
L'invention concerne une composition destinée à la fabrication d'un matériau solide comprenant une résine polymérique de type résine polyester orthophtalique ainsi qu'une charge inerte comprenant une charge de remplissage poreuse de densité moyenne et de diamètre granulométrique variable comportant de préférence deux charges de diamètre granulométrique moyen différent ainsi qu'une charge isolante constituée de microsphères de verre creuses en proportion en poids substantiellement inférieure à la proportion en poids de la charge de remplissage. Cette composition, lorsqu'utilisée dans le domaine sanitaire, offre une résistance mécanique et des propriétés d'isolations thermique et phonique importantes obtenues grâce à sa forte densité, obtenue sans augmentation de poids, par la sélection de la nature ainsi que de la granulométrie de ses composantes et par l'adjonction de charges d'air situées à l'intérieur des microsphères de verre et qui permettent de conserver la chaleur de l'eau. Bien que les applications principales de la composition de l'invention se situent dans le domaine sanitaire, son utilisation est également envisagée dans le domaine du bâtiment, dans la fabrication d'entablements ou de mobilier. De façon générale, les domaines d'application s'étendent à la fabrication de tout type de matériau nécessitant un état de surface dense et lisse. Afin de pouvoir obtenir un matériau présentant les propriétés souhaitées, le choix du type et de la proportion de ses composantes principales, soit la résine de coulée, la charge de remplissage ainsi que la charge isolante, doit être effectué avec soin.The invention relates to a composition intended for the manufacture of a solid material comprising a polymeric resin of the orthophthalic polyester resin type as well as an inert filler comprising a porous filler of medium density and of variable particle size diameter preferably comprising two fillers. different mean particle size diameter as well as an insulating charge consisting of hollow glass microspheres in proportion by weight substantially less than the proportion by weight of the filling charge. This composition, when used in the sanitary field, offers mechanical strength and significant thermal and phonic insulation properties obtained thanks to its high density, obtained without increase in weight, by the selection of the nature as well as the particle size of its components and by the addition of air charges located inside the glass microspheres and which conserve the heat of the water. Although the main applications of the composition of the invention are in the sanitary field, its use is also envisaged in the building field, in the manufacture of tables or furniture. In general, the fields of application extend to the manufacture of any type of material requiring a dense and smooth surface condition. In order to be able to obtain a material having the desired properties, the choice of the type and the proportion of its main components, namely the casting resin, the filling filler as well as the insulating filler, must be made with care.
Résine de couléeCasting resin
Le type de résine pouvant être utilisé dans les compositions de l'invention est très variable et son choix peut facilement être effectué par la personne versée dans l'art qui prendrait en compte un certain nombre de critères de sélection. Tel que mentionné précédemment, la résine utilisée dans la composition de l'invention doit idéalement posséder une bonne mouillabilité de charge, ainsi qu'une bonne résistance mécanique. De plus, la résine polymérique devrait être caractérisée par une absence de chauffage lors de sa polymérisation, ceci ayant pour but d'éviter d'affecter les moules utilisés dans la fabrication du matériau solide.The type of resin that can be used in the compositions of the invention is very variable and its choice can easily be made by the person skilled in the art who would take into account a certain number of selection criteria. As mentioned above, the resin used in the composition of the invention should ideally have good filler wettability, as well as good mechanical strength. In addition, the polymeric resin should be characterized by an absence of heating during its polymerization, this having the aim of avoiding affecting the molds used in the manufacture of the solid material.
De plus, puisqu'une des utilisations principales de la composition de l'invention est le domaine sanitaire, la résine polymérique utilisée ne devrait pas se déformer sous la chaleur de façon substantielle.In addition, since one of the main uses of the composition of the invention is in the sanitary field, the polymeric resin used should not deform under heat substantially.
De façon générale, la résine de coulée utilisée dans la composition de la présente invention est une résine de polyester et/ou de vinylester insaturé. De telles résines ont l'avantage d'avoir des temps de séchage courts ainsi que d'excellentes propriétés adhésives. De façon préférée, la résine de coulée est une résine polyester orthophtalique du type sterpon 3780-15 commercialisée par la société CONVERT. La proportion de résine utilisée dans la composition de l'invention peut varier entre 20 et 60% en poids, notamment entre 50 et 60% en poids. Bien qu'il soit souhaitable d'utiliser aussi peu de résine que possible, un pourcentage variant entre 50 et 60% est préférable pour pouvoir obtenir la rigidité et l'adhésion voulues. Charges inertes a) Charges de remplissageGenerally, the casting resin used in the composition of the present invention is an unsaturated polyester and / or vinylester resin. Such resins have the advantage of having short drying times as well as excellent adhesive properties. Preferably, the casting resin is an orthophthalic polyester resin of the sterpon 3780-15 type sold by the company CONVERT. The proportion of resin used in the composition of the invention can vary between 20 and 60% by weight, in particular between 50 and 60% by weight. Although it is desirable to use as little resin as possible, a percentage varying between 50 and 60% is preferable in order to be able to obtain the desired rigidity and adhesion. Inert charges a) Filling charges
La nature ainsi que la proportion de la charge de remplissage utilisée constitue un des éléments importants de la présente invention. En effet, les inventeurs ont noté que le choix d'une charge de remplissage possédant un diamètre granulométrique variable couplé à l'utilisation de microsphères dont les propriétés essentielles seront décrites en détail plus loin, a permis d'améliorer de façon notable l'état de surface du matériau fabriqué à partir de la composition de l'invention.The nature as well as the proportion of the filling charge used constitutes one of the important elements of the present invention. In fact, the inventors have noted that the choice of a filling filler having a variable particle size diameter coupled with the use of microspheres whose essential properties will be described in detail below, has made it possible to significantly improve the condition surface of the material made from the composition of the invention.
De façon préférable, la charge de remplissage est une charge poreuse pouvant absorber une certaine quantité de résine à l'état liquide et ayant une densité moyenne. Il s'agit généralement de charges inorganiques de type carbonate de calcium, ou argile. Les charges de type carbonate de calcium sont préférées en raison de leur faible coût et de la possibilité d'obtenir facilement un grand nombre de granulométries différentes. Une des réalisations préférentielles de l'invention prévoit l'utilisation de deux charges de remplissage de diamètres granulométriques moyens différents, se situant entre 1 et 500 μm. Des quantités élevées de charges de remplissage de diamètre moyen inférieur à 100 ne sont pas souhaitables. Le pourcentage en poids de la charge de remplissage étant relativement élevé, les diamètres granulométriques très faibles donnent des compositions à densité trop élevée donc trop lourdes. La charge de remplissage est idéalement constituée d'environ 13 à 14% en poids de carbonate de calcium de diamètre moyen variant entre 1 et 200 μm et d'environ 26 à 27% de carbonate de calcium de diamètre variant entre 100 et 500 μm. Des exemples typiques de carbonate de calcium utilisé dans le contexte de la présente invention incluent des carbonates de calcium commercialisés par la société OMYA sous les marques Durcal 30, Durcal 40 et Durcal 130. Une quantité minimale de charge de remplissage de l'ordre d'environ 30% est nécessaire pour pouvoir obtenir une composition ayant les propriétés désirées. Cette quantité minimale peut difficilement être remplacée soit par des microsphères de verre, soit par une quantité additionnelle de résine. Une quantité élevée de microsphères de verre augmente considérablement le coût de la composition. En ce qui concerne la résine, l'utilisation de quantités importantes cause des problèmes de chauffe des moules et de façon plus importante, les résines à polymérisation rapide ont tendance à se fissurer lors du séchage. L'utilisation d'une quantité minimale de charges de remplissage permet à ces dernières d'agir à titre d'amortisseur de polymérisation et d'éviter ainsi les problèmes de chauffe et de craquement de la résine. De plus, l'utilisation d'une charge de remplissage permet de diminuer l'effet de retrait observé lors du séchage de la résine, b) charge isolantePreferably, the filling filler is a porous filler capable of absorbing a certain quantity of resin in the liquid state and having a medium density. They are generally inorganic fillers of the calcium carbonate or clay type. Fillers of the calcium carbonate type are preferred because of their low cost and the possibility of easily obtaining a large number of different particle sizes. One of the preferred embodiments of the invention provides for the use of two filling charges of different mean particle size diameters, lying between 1 and 500 μm. Large amounts of fillers with an average diameter of less than 100 are not desirable. The percentage by weight of the filling filler being relatively high, the very small particle size diameters give compositions with too high a density therefore too heavy. The filling charge is ideally made up of approximately 13 to 14% by weight of calcium carbonate of average diameter varying between 1 and 200 μm and approximately 26 to 27% of calcium carbonate of diameter varying between 100 and 500 μm. Typical examples of calcium carbonate used in the context of the present invention include carbonates of calcium sold by the company OMYA under the brands Durcal 30, Durcal 40 and Durcal 130. A minimum quantity of filler of the order of approximately 30% is necessary in order to be able to obtain a composition having the desired properties. This minimum quantity can hardly be replaced either by glass microspheres or by an additional quantity of resin. A high amount of glass microspheres considerably increases the cost of the composition. As far as the resin is concerned, the use of large quantities causes problems with the heating of the molds and more importantly, the quick-curing resins tend to crack during drying. The use of a minimum quantity of fillers allows these fillers to act as a polymerization damper and thus avoid the problems of heating and cracking of the resin. In addition, the use of a filling filler makes it possible to reduce the shrinking effect observed during the drying of the resin, b) insulating filler
La charge isolante est constituée de microsphères de verre creuses dont la proportion en poids varie entre 1 et 10%, notamment entre 1 et 4%. Bien que la proportion de microsphères de verre creuses présentes dans la composition de l'invention soit assez faible, cette proportion s'est avérée suffisante pour conférer des propriétés accrues d'isolations thermique et phonique au matériau de l'invention lorsque comparé à un matériau du même type ne comprenant pas de microsphères. Les propriétés d'isolation thermique sont bien sûr particulièrement désirables dans le domaine sanitaire.The insulating filler consists of hollow glass microspheres whose proportion by weight varies between 1 and 10%, in particular between 1 and 4%. Although the proportion of hollow glass microspheres present in the composition of the invention is quite low, this proportion has been found to be sufficient to confer increased thermal and sound insulation properties on the material of the invention when compared to a material of the same type not comprising microspheres. The thermal insulation properties are of course particularly desirable in the sanitary field.
De plus, l'utilisation de microsphères de verre creuses couplées à une charge de remplissage adéquate permet la fabrication d'un matériau ayant une résistance mécanique suffisamment importante pour pouvoir l'utiliser dans certaines applications sans qu'il soit recouvert d'un support de renfort solide tel un support de fibres de verre imprégné de résine polymérique, Ceci n'aurait pas été possible avec les matériaux décrits dans l'art antérieur. Ce phénomène résulte donc de la combinaison d'un pourcentage en poids d'au moins 40% d'une charge de remplissage de diamètre granulométrique moyen variable d'au moins 40%, notamment de charge à un faible pourcentage de charge isolante constituée de microsphères de verre creuses.In addition, the use of hollow glass microspheres coupled with an adequate filling load allows the manufacture of a material having a mechanical strength sufficiently high to be able to use it in certain applications without it being covered with a support. solid reinforcement such as a glass fiber support impregnated with polymeric resin, This would not have been possible with the materials described in the prior art. This phenomenon therefore results from the combination of a percentage by weight of at least 40% of a filling filler of variable mean particle size diameter of at least 40%, in particular of charging with a small percentage of insulating filler consisting of microspheres of hollow glass.
On retrouve un certain nombre de types de microsphères creuses présentement disponibles dans le commerce. Cependant, on choisira de préférence des microsphères ayant une faible densité nominale, de l'ordre de 0,1 à 0,3 g/cm3. Les microsphères de densité faible sont choisies en raison de leur faible poids et de leur volume élevé qui favorise une adjonction de charge d'air plus élevée, augmentant ainsi les propriétés de conservation de chaleur du matériau obtenu. A titre d'exemples, les microsphères commercialisées sous la référence K1 , K15, K20 ou K25 par la société 3M sont notamment utilisées en proportion en poids variant de 1 à 10% mais plus particulièrement en proportion en poids variant de 1 à 4%. Composantes additionnellesThere are a number of types of hollow microspheres currently available commercially. However, microspheres having a low nominal density, of the order of 0.1 to 0.3 g / cm 3 , will preferably be chosen. The low density microspheres are chosen because of their low weight and their large volume which favors the addition of a higher air charge, thus increasing the heat conservation properties of the material obtained. By way of examples, the microspheres sold under the reference K1, K15, K20 or K25 by the company 3M are in particular used in proportion by weight varying from 1 to 10% but more particularly in proportion by weight varying from 1 to 4%. Additional components
La composition de l'invention peut également comprendre un catalyseur pour la polymérisation de la résine de coulée. Le choix du catalyseur approprié fait partie des connaissances de l'homme du métier.The composition of the invention may also comprise a catalyst for the polymerization of the casting resin. The choice of the appropriate catalyst is part of the knowledge of a person skilled in the art.
A titre d'exemple, les catalyseurs de type peroxyde de méthyléthylcétone tels que les catalyseurs commercialisés par la société AKZO sous la marque Butanox et plus particulièrement sous la marque Butanox M-50 peuvent être utilisés. De plus, il peut être souhaitable d'utiliser des accélérateurs favorisant le durcissement des résines polyester insaturés à température ambiante. Des accélérateurs de type octanoate de cobalt, également commercialisés par la société AKZO sous les marques Accélérateur NL51 P ou Accélérateur NL51 S constituent des accélérateurs de choix. Matériau compositeBy way of example, catalysts of the methyl ethyl ketone peroxide type such as the catalysts sold by the company AKZO under the brand Butanox and more particularly under the brand Butanox M-50 can be used. In addition, it may be desirable to use accelerators that promote the curing of unsaturated polyester resins at room temperature. Cobalt octanoate accelerators, also sold by AKZO under the brands Accelerator NL51 P or Accelerator NL51 S, are the accelerators of choice. Composite material
La présente invention concerne également un matériau composite comprenant la composition décrite précédemment ainsi qu'un support de renfort solide en recouvrant la surface extérieure. L'utilisation d'un support de renfort solide peut s'avérer essentiel dans certaines applications. En effet, la composition de l'invention demeure d'abord et avant tout une substance coulable. Bien que les inventeurs aient démontré qu'il est possible de l'utiliser sans support de renfort dans certaines applications, ce qui s'avérait impossible précédemment, tant au niveau de la faible résistance mécanique des compositions de l'art antérieur que de l'absence d'une surface extérieure non poreuse, de meilleurs rendements sont obtenus lorsqu'un support de renfort solide est appliqué sur la surface extérieure.The present invention also relates to a composite material comprising the composition described above as well as a solid reinforcement support covering the exterior surface. The use of a solid reinforcement support may prove essential in certain applications. Indeed, the composition of the invention remains first and foremost a flowable substance. Although the inventors have demonstrated that it is possible to use it without reinforcing support in certain applications, which previously proved impossible, both in terms of the low mechanical resistance of the compositions of the prior art and of absence of a non-porous exterior surface, better yields are obtained when a solid reinforcement support is applied to the exterior surface.
On peut envisager l'utilisation d'un seul support de renfort ou encore d'une combinaison de divers renforts qui permettent d'obtenir un revêtement extérieur lisse et très solide. Dans les paragraphes suivants, quelques exemples de supports de renfort sont énumérés. La personne versée dans l'art pourra cependant choisir d'autres types de support sans difficulté, simplement en faisant appel à ses connaissances techniques. Supports de renfortWe can consider the use of a single reinforcement support or of a combination of various reinforcements which make it possible to obtain a smooth and very solid external coating. In the following paragraphs, some examples of reinforcement supports are listed. The person skilled in the art will however be able to choose other types of support without difficulty, simply by calling on his technical knowledge. Reinforcement supports
Un des matériaux de choix utilisés à titre de support de renfort comprend une couche de fibres de verre stratifiée imprégnée d'une résine polymérique. Les fibres de verre stratifiées peuvent prendre la forme de feutres de fils de verre coupés et agglomérés par un liant liquide à haute solubilité dans le styrène. La fibre de verre doit être souple, posséder une grande facilité de manipulation et pouvoir être imprégnée de résine polyester sans difficulté. Un exemple du type de fibre de verre qui peut être utilisée dans le contexte de la présente invention est le Mat M4 commercialisé par la société VETROTEX. La masse surfacique du support de fibres de verre stratifié varie généralement entre 1000 et 1500 g/m2. De façon préférée, la fibre de verre stratifiée possède une masse surfacique d'environ 1200 g/m2. En ce qui concerne l'épaisseur de la couche de fibres de verre stratifiée, celle-ci pourra être variée suivant les applications désirées. Dans le domaine sanitaire, l'épaisseur de la couche de fibres de verre varie entre 0,5 et 1 ,5 MM. De façon préférée, l'épaisseur de la couche de fibres de verre stratifiée est d'environ 1 MM.One of the materials of choice used as a reinforcing support comprises a layer of laminated glass fibers impregnated with a polymeric resin. The laminated glass fibers can take the form of felt glass fibers cut and agglomerated by a liquid binder with high solubility in styrene. The fiberglass must be flexible, have great ease of handling and be able to be impregnated with polyester resin without difficulty. An example of the type of glass fiber which can be used in the context of the present invention is Mat M4 sold by the company VETROTEX. The surface mass of the laminated glass fiber support generally varies between 1000 and 1500 g / m 2 . Preferably, the fiber of laminated glass has a basis weight of approximately 1200 g / m 2 . As regards the thickness of the layer of laminated glass fibers, this may be varied according to the desired applications. In the sanitary field, the thickness of the layer of glass fibers varies between 0.5 and 1.5 mm. Preferably, the thickness of the layer of laminated glass fibers is approximately 1 MM.
Dans certaines applications des compositions de l'invention, l'utilisation de renforts solides en complément ou en remplacement des fibres de verre est également envisagée. A cet égard, des substances solidifiantes de type Gelcoat permettant d'obtenir un film de surface souple, dur et brillant supportant avec succès des tests de vieillissement, peuvent être utilisées.In certain applications of the compositions of the invention, the use of solid reinforcements in addition to or in replacement of glass fibers is also envisaged. In this regard, solidifying substances of the Gelcoat type making it possible to obtain a flexible, hard and shiny surface film successfully supporting aging tests, can be used.
Des exemples de ce type de substances incluent des formules à base d'acide isophtalique et de néoantylglycol tels que le Gelcoat Sterpon 40 commercialisé par la société CONVERT. L'épaisseur de ce type de revêtement varie normalement entre 0,4 mm et 0,6 mm et de façon préférée est d'environ 0,5 mm.Examples of this type of substance include formulas based on isophthalic acid and neoantylglycol such as the Gelcoat Sterpon 40 sold by the company CONVERT. The thickness of this type of coating normally varies between 0.4 mm and 0.6 mm and preferably is around 0.5 mm.
Procédé de fabrication de la composition et du matériau de l'invention La chronologie de fabrication de la composition de la présente invention correspond à la chronologie présentement utilisée par la personne versée dans l'art pour la fabrication de compositions du même type. Cette chronologie ne sera que légèrement modifiée en fonction de l'utilisation ou non d'un support de renfort solide. Lorsqu'il s'agit de préparer une composition de l'invention utilisée sans support de renfort solide, on mélange d'abord la résine à l'accélérateur. La charge inerte est ensuite incorporée au mélange. Bien qu'il ne soit pas absolument nécessaire de s'en tenir à un ordre précis, il est préférable d'incorporer d'abord la charge de remplissage poreuse de plus faible diamètre granulométrique, suivie de la charge de remplissage poreuse de diamètre granulométrique plus élevé pour terminer avec l'incorporation de la charge isolante constituée de microsphères de verre creuses. On incorpore ensuite le catalyseur puis on effectue le mélange de la composition jusqu'à l'obtention d'une substance homogène. Le mélange est ensuite coulé par gravité entre un moule et un contre-moule. La coulée est suivie d'une période de séchage plus ou moins longue qui sera fonction du catalyseur utilisé.Process for manufacturing the composition and the material of the invention The production timeline for the composition of the present invention corresponds to the timeline currently used by the person skilled in the art for the manufacture of compositions of the same type. This chronology will only be slightly modified according to the use or not of a solid reinforcement support. When it is a question of preparing a composition of the invention used without a solid reinforcement support, the resin is first mixed with the accelerator. The inert filler is then incorporated into the mixture. Although it is not absolutely necessary to stick to a precise order, it is preferable to incorporate first the porous filler of smaller particle size diameter, followed by the porous filler of smaller particle size diameter high to finish with the incorporation of the insulating filler made up of hollow glass microspheres. The catalyst is then incorporated and the composition is then mixed until a homogeneous substance is obtained. The mixture is then poured by gravity between a mold and a counter-mold. The casting is followed by a more or less long drying period which will depend on the catalyst used.
De façon générale, il est nécessaire d'effectuer le mélange des divers éléments de la coulée pour une période variant entre 10 et 30 mn et de façon préférable pour une période d'environ 25 mn pour obtenir un mélange homogène. La coulée doit normalement s'effectuer entre 5 et 10 mn après l'incorporation du catalyseur dans la coulée, bien que cette période puisse également être variée en fonction du catalyseur utilisé. Dans l'état actuel des connaissances, le temps de séchage requis pour observer une solidification suffisante du mélange varie généralement entre 30 et 90 mn.Generally, it is necessary to mix the various elements of the casting for a period varying between 10 and 30 min and preferably for a period of about 25 min to obtain a homogeneous mixture. The casting should normally take place between 5 and 10 min after the incorporation of the catalyst into the casting, although this period may also be varied depending on the catalyst used. In the current state of knowledge, the drying time required to observe sufficient solidification of the mixture generally varies between 30 and 90 min.
Lorsque la composition de la présente invention est recouverte d'un support de renfort solide constitué de fibres de verre, ces dernières sont appliquées sur les moules avant la coulée. La coulée n'est introduite dans les moules qu'après le séchage du support de fibres de verre.When the composition of the present invention is covered with a solid reinforcing support consisting of glass fibers, the latter are applied to the molds before casting. The casting is only introduced into the molds after the glass fiber support has dried.
Il existe plusieurs méthodes de stratification manuelle de fibres de verre, soit directement sur le moule lorsque les fibres de verre constituent le seul support de renfort solide, soit sur un matériau de type Gelcoat lorsque ce type de matériau est utilisé. On peut soit appliquer des couches successives de résine et de renfort de verre à l'intérieur d'un moule ouvert, soit projeter simultanément les fibres de verre et la résine sur un moule ouvert, soit pulvériser ou déposer la résine catalysée sur un lit de fibres de verre ou de mat en continu. Toutes ces techniques d'imprégnation sont connues de la personne versée dans l'art qui pourra choisir la technique convenant le mieux à l'application envisagée. ExemplesThere are several methods of manual laminating of glass fibers, either directly on the mold when the glass fibers constitute the only solid reinforcement support, or on a Gelcoat type material when this type of material is used. One can either apply successive layers of resin and glass reinforcement inside an open mold, or simultaneously spray the glass fibers and the resin on an open mold, or spray or deposit the catalyzed resin on a bed of continuous glass or mat fibers. All these impregnation techniques are known to the person skilled in the art who can choose the technique best suited to the intended application. Examples
1 ) Fabrication d'une coulée1) Making a casting
On mélange à un kilogramme de résine orthophtalique de marque Convert (référence Sterpon 3780-15), 240 g de charge de remplissage poreuse à faible diamètre granulométrique commercialisée par la société OMYA sous la référence Durcal 40 et 460 g de charge de remplissage poreuse de diamètre élevé commercialisé par la société OMYA sous la référence Durcal 130 et 35 g de charge de microsphères de verre creuses de type K1 commercialisées par la société 3M. Un accélérateur à base d'octanoate de cobalt à 6% et un catalyseur contenant240 g of orthophthalic resin of the Convert brand (reference Sterpon 3780-15) are mixed with 240 g of porous filler with a small particle size diameter sold by the company OMYA under the reference Durcal 40 and 460 g of porous filler with diameter high marketed by the company OMYA under the Durcal reference 130 and 35 g of charge of hollow glass microspheres of type K1 marketed by the company 3M. A 6% cobalt octanoate accelerator and a catalyst containing
50% de peroxyde de méthyléthylcétone. Le pourcentage de catalyseur est d'environ 1 à 2%.50% methyl ethyl ketone peroxide. The percentage of catalyst is approximately 1 to 2%.
La coulée est effectuée dans un moule approprié à la température ambiante et la composition ainsi obtenue est séchée pour une période d'environ 12 heures pour éviter toutes déformations avant d'être démoulée.The casting is carried out in a suitable mold at room temperature and the composition thus obtained is dried for a period of approximately 12 hours to avoid any deformation before being demolded.
2) Préparation d'un matériau comprenant la composition de l'exemple 1 recouverte d'un support de renfort solide.2) Preparation of a material comprising the composition of Example 1 covered with a solid reinforcement support.
La fabrication d'un tel matériau est effectuée en trois étapes. II s'agit d'abord d'appliquer environ 0,5 mm d'un Gelcoat sanitaire de qualité isophtalique tel que le Gelcoat Sterpon 4040 commercialisé par la société CONVERT S.A.. Une fois le Gelcoat séché, un mat de verre ayant une masse surfacique de 300 g/m2 et imbibé d'une résine polyester isophtalique est appliqué sur la surface du moule, en utilisant une méthode de moulage au contact. L'épaisseur de ce deuxième revêtement est d'environ 1 mm.The manufacture of such a material is carried out in three stages. It is firstly a question of applying approximately 0.5 mm of a sanitary gelcoat of isophthalic quality such as the Gelcoat Sterpon 4040 marketed by the company CONVERT SA. Once the Gelcoat has dried, a glass mat having a surface mass of 300 g / m 2 and impregnated with an isophthalic polyester resin is applied to the surface of the mold, using a contact molding method. The thickness of this second coating is approximately 1 mm.
Après le séchage de cette couche de fibres de verre stratifiée, les deux parties du moule sont assemblées et la résine de coulée fabriquée à l'exemple 1 est coulée par gravité entre le moule et le contre-moule. L'ensemble est ensuite séché puis démoulé. After this layer of laminated glass fibers has dried, the two parts of the mold are assembled and the casting resin produced in Example 1 is poured by gravity between the mold and the counter-mold. The whole is then dried and then removed from the mold.

Claims

REVENDICATIONS
1. Composition destinée à la fabrication d'un matériau solide, notamment de matériaux utilisés dans le domaine sanitaire, ladite composition étant caractérisée en ce qu'elle comprend : - une résine polymérique de coulée présentant des caractéristiques de mouillabilité de charge, de résistance mécanique, de faible chauffage lors de sa polymérisation et d'absence de déformation sous la chaleur une fois solidifiée ; et1. Composition intended for the manufacture of a solid material, in particular of materials used in the sanitary field, said composition being characterized in that it comprises: - a polymeric casting resin having characteristics of wettability of load, of mechanical resistance , weak heating during its polymerization and absence of deformation under heat once solidified; and
- une charge inerte ne réagissant pas avec les substances entrant dans la composition de ladite résine polymérique, ladite charge comprenant :an inert filler which does not react with the substances used in the composition of said polymeric resin, said filler comprising:
• une charge de remplissage poreuse de densité moyenne, notamment de type carbonate de calcium, possédant un diamètre granulométrique moyen variable, ladite charge de remplissage étant notamment constituée de deux charges de diamètre granulométrique moyen différent, notamment supérieur à environ 1 μm et inférieur à environ 500 μm ; et• a porous filling filler of medium density, in particular of the calcium carbonate type, having a variable mean particle size diameter, said filling filler consisting in particular of two fillers of different average particle size diameter, in particular greater than approximately 1 μm and less than approximately 500 μm; and
• une charge isolante comprenant des microsphères de verre creuses en proportion en poids substantiellement inférieure à la proportion en poids de la charge de remplissage présente dans ledit matériau, la quantité ainsi que le type de charge de remplissage poreuse ainsi que la quantité de charge isolante, notamment de type microsphères de verre creuses, présentes dans ledit matériau étant suffisantes pour conférer audit matériau un état de surface lisse et dense et une résistance mécanique ainsi que des caractéristiques d'isolations thermique et phonique accrues lorsque comparées à un matériau du même type comprenant une charge de remplissage unique et/ou ne comprenant pas de charge isolante, notamment de type microsphères.An insulating filler comprising hollow glass microspheres in proportion by weight substantially lower than the proportion by weight of the filling filler present in said material, the quantity as well as the type of porous filling filler as well as the quantity of insulating filler, in particular of the hollow glass microspheres type, present in said material being sufficient to confer on said material a smooth and dense surface condition and a mechanical resistance as well as increased thermal and sound insulation characteristics when compared to a material of the same type comprising a single filling filler and / or not comprising an insulating filler, in particular of the microsphere type.
2. Composition selon la revendication 1 , caractérisée en ce qu'elle comprend entre 1 et 10%, notamment entre 1 et 4% en poids de microsphères de verre creuses. 2. Composition according to claim 1, characterized in that it comprises between 1 and 10%, in particular between 1 and 4% by weight of hollow glass microspheres.
3. Composition selon la revendication 1 ou 2, caractérisée en ce que le diamètre des microsphères de verre creuses varie entre 5 et 200 μm, notamment entre 10 et 100 μm.3. Composition according to claim 1 or 2, characterized in that the diameter of the hollow glass microspheres varies between 5 and 200 μm, in particular between 10 and 100 μm.
4. Composition selon l'une quelconque des revendications 1 à 3, caractérisée en ce que la proportion en poids de charge de remplissage varie entre 30 et 79%, notamment entre 39 et 79%.4. Composition according to any one of claims 1 to 3, characterized in that the proportion by weight of filling filler varies between 30 and 79%, in particular between 39 and 79%.
5. Composition selon l'une quelconque des revendications 1 à 4, caractérisée en ce que la charge de remplissage est constituée de deux charges présentant des diamètres granulométriques moyens respectifs différents variant entre 1 et 300 μm et entre 100 et 500 μm.5. Composition according to any one of claims 1 to 4, characterized in that the filling charge consists of two fillers having different mean particle size diameters varying between 1 and 300 μm and between 100 and 500 μm.
6. Composition selon la revendication 5, caractérisée en ce que la charge de remplissage est constituée de 10 à 15 % en poids de carbonate de calcium de diamètre moyen variant entre 1 et 200 μm et de 25 à 30% de carbonate de calcium de diamètre moyen variant entre 100 et 500 μm.6. Composition according to claim 5, characterized in that the filling charge consists of 10 to 15% by weight of calcium carbonate of average diameter varying between 1 and 200 μm and of 25 to 30% of calcium carbonate of diameter medium varying between 100 and 500 μm.
7. Composition selon l'une quelconque des revendications 1 à 6, caractérisée en ce que la résine polymérique de coulée est une résine polyester orthophtalique.7. Composition according to any one of claims 1 to 6, characterized in that the polymeric casting resin is an orthophthalic polyester resin.
8. Composition selon la revendication 7, caractérisée en ce que le pourcentage en poids de la résine polyester orthophtalique varie entre 20% et 60%, notamment entre 50% et 60%.8. Composition according to claim 7, characterized in that the percentage by weight of the orthophthalic polyester resin varies between 20% and 60%, in particular between 50% and 60%.
9. Composition selon l'une quelconque des revendications 1 à 8, caractérisée en ce qu'une fois solidifiée, elle présente une épaisseur variant entre 5 mm et 5 cm. 9. Composition according to any one of claims 1 to 8, characterized in that once solidified, it has a thickness varying between 5 mm and 5 cm.
10. Matériau composite caractérisé en ce qu'il comprend :10. Composite material characterized in that it comprises:
- une composition selon l'une quelconque des revendications 1 à 9 ;- a composition according to any one of claims 1 to 9;
- un support de renfort solide recouvrant la surface extérieure de ladite composition. - A solid reinforcement support covering the outer surface of said composition.
11. Matériau selon la revendication 10, caractérisé en ce que le support solide comprend une couche de fibre de verre stratifiée imprégnée d'une résine polymérique.11. Material according to claim 10, characterized in that the solid support comprises a layer of laminated glass fiber impregnated with a polymeric resin.
12. Matériau selon la revendication 11, caractérisé en ce que ladite fibre de verre stratifiée incluant la résine possède une masse surfacique de 1000 à 1500 g/m2 12. Material according to claim 11, characterized in that said laminated glass fiber including the resin has a surface mass of 1000 to 1500 g / m 2
13. Matériau selon la revendication 11 ou 12, caractérisé en ce que la couche de fibre de verre stratifiée a une épaisseur variant entre 0,5 et 1,5 mm. 13. Material according to claim 11 or 12, characterized in that the layer of laminated glass fiber has a thickness varying between 0.5 and 1.5 mm.
14. Matériau selon l'une quelconque des revendications 11 à14. Material according to any one of claims 11 to
13, caractérisé en ce que le support de renfort solide comprend également un recouvrement de type Gelcoat.13, characterized in that the solid reinforcement support also includes a Gelcoat type covering.
15. Matériau selon la revendication 14, caractérisé en ce que l'épaisseur du Gelcoat varie entre 0,4 et 0,6 mm. 15. Material according to claim 14, characterized in that the thickness of the gelcoat varies between 0.4 and 0.6 mm.
PCT/FR1996/000752 1995-05-19 1996-05-20 Composition for producing solid materials, particularly sanitary ware WO1996036664A1 (en)

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FR95/06003 1995-05-19
FR9506003A FR2734271B1 (en) 1995-05-19 1995-05-19 COMPOSITION FOR THE MANUFACTURE OF SOLID MATERIALS, IN PARTICULAR FOR USE IN THE MANUFACTURE OF SANITARY OBJECTS

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103087463A (en) * 2013-01-28 2013-05-08 奇瑞汽车股份有限公司 Light composite material
CN108641285A (en) * 2018-03-30 2018-10-12 张贞霞 A kind of sanitaryware and preparation method thereof
CN113831891A (en) * 2021-08-31 2021-12-24 广州集泰化工股份有限公司 Ultra-light heat-insulation pouring sealant and preparation method and application thereof

Citations (4)

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Publication number Priority date Publication date Assignee Title
US4053448A (en) * 1976-06-21 1977-10-11 Arthur William Holle Polyester based patching composition
GB2114466A (en) * 1981-12-12 1983-08-24 Twyfords Ltd Manufacture of articles of reinforced acrylic sheet material
DE3844284C1 (en) * 1988-12-30 1990-04-05 Gurit-Essex Ag, Freienbach, Ch
EP0725105A1 (en) * 1995-02-06 1996-08-07 SOCIETE CIVILE NEURONE Société Civile dite : Unsaturated polyester composition for sanitary products

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4053448A (en) * 1976-06-21 1977-10-11 Arthur William Holle Polyester based patching composition
GB2114466A (en) * 1981-12-12 1983-08-24 Twyfords Ltd Manufacture of articles of reinforced acrylic sheet material
DE3844284C1 (en) * 1988-12-30 1990-04-05 Gurit-Essex Ag, Freienbach, Ch
EP0725105A1 (en) * 1995-02-06 1996-08-07 SOCIETE CIVILE NEURONE Société Civile dite : Unsaturated polyester composition for sanitary products

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103087463A (en) * 2013-01-28 2013-05-08 奇瑞汽车股份有限公司 Light composite material
CN108641285A (en) * 2018-03-30 2018-10-12 张贞霞 A kind of sanitaryware and preparation method thereof
CN113831891A (en) * 2021-08-31 2021-12-24 广州集泰化工股份有限公司 Ultra-light heat-insulation pouring sealant and preparation method and application thereof

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Publication number Publication date
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FR2734271B1 (en) 1997-07-18

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