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    • 专利摘要:
    There is disclosed a method of manufacturing an article for covering floors or walls, comprising the following steps, performed in a mold: a) optionally applying a gelcoat layer based on a first curing polymer resin to the inside of the mold in order to obtain a coated mold, b) introducing into the core of the mold or of the coated mold a filler composition based on a second curing polymer resin, supplemented with at least one mineral filler material, characterized in that the core of the article has a thickness of at least 10mm, the core filler composition contains at least 5% by weight and at most 20% by weight of curing polymer resin, relative to the dry amount of the filler composition, and the filler composition contains only a single initiator at a concentration of 0.5% by weight to 5.0% by weight in proportion to the amount of curing polymer resin in the filler composition.
    公开号:BE1026291B1
    申请号:E20195327
    申请日:2019-05-17
    公开日:2019-12-19
    发明作者:Alexandre Moreels
    申请人:Polysto；
    IPC主号:
    专利说明:

    Improvement of wall and wall covering elements
    SCOPE OF THE INVENTION
    The present invention relates to an improved method for the manufacture of elements intended for coating surfaces in construction. More particularly, the invention relates to the production of protective elements, such as skirting boards and bumpers, which are suitable for use in areas where hygiene is important, such as in the food industry, in the pharmaceutical industry, in hospitals or in clean rooms, such as, for example, in the electronic industry.
    BACKGROUND OF THE INVENTION
    It is known to provide protective elements such as skirting boards and bumpers at the places where walls and floors merge. These elements can mechanically protect the underside of the walls, as well as indirectly the walls above them, against shocks and bumps by trolleys, carts, forklift trucks, pallet trucks, pump trucks or pallet trucks, also sometimes called transport pallets, or also by mobile equipment or furniture, such as serving trolleys or hospital beds. The corners of passageways are particularly vulnerable, and such protection is therefore very important there.
    The more traditional skirting boards, which are usually made of wood, plastic or light metal, cannot be used in many environments because they do not offer sufficient strength and / or wear resistance, easily deform, and do not meet the hygienic requirements associated with the function of the building in which they are used, or do not display the appropriate aesthetic appearance.
    More robust skirting boards can be made from concrete, but this material is relatively brittle and crumbling
    BE2019 / 5327 is easily finished, generally has a certain porosity and is not water-repellent, so that these skirting boards are also undesirable from a hygienic point of view.
    For that reason, such concrete bumps are often provided with a metal coating on the outside, at least partially but preferably over the entire visible surface. Stainless steel is often used for this, because it gives a more hygienic and aesthetic appearance and also retains that for a long time. In order to improve the adhesion of the steel outer layer to the concrete, the metal coating can be formed such that, for a better anchoring, it grips the concrete core and / or an edge thereof can be embedded in the concrete core. Such an embodiment is described in German Patent Specification DE 4340953 C1, in which a filling part consisting of polystyrene foam is used to reduce the weight of the product. The metal layer can also be glued to improve the adhesion of the steel outer layer to the concrete. Such skirting boards are described, inter alia, in Belgian patent BE 1017613 A6. However, applying this additional metal coating is cumbersome.
    DE 2619058 A1 describes a similar embodiment with a core of polyurethane foam (PU foam). This foam can be given an appropriate rigidity and elasticity to support the outer metal layer, to protect it against deformations in the event of impact, and even to provide a certain damping and flexibility.
    In all described applications, this additional metal coating represents a considerable additional cost in the use of materials and requires additional steps in the production process.
    In addition, the butt joints of the skirting boards,
    i.e. the sides where two consecutive skirting boards approach each other, in most of these embodiments still remain uncovered, so that they are still fairly rough and inaccurately finished. When placing the bumpers, this leads to wider joints, which is undesirable because dirt is more easily deposited there and because they also require more material to be filled.
    BE2019 / 5327
    Skirting boards have also been developed based on less brittle materials than concrete. Plastics can be used as binders for the core of such skirting boards, preferably supplemented with one or more filling materials. The binders are preferably polymeric resins that cure by crosslinking such that they form a solid three-dimensional molecular structure. In this way they offer good adhesion to the filling materials and a solid structure. These resins are preferably also water-repellent, such that the skirting boards can also meet some of the hygienic requirements.
    In EP 848120 A1 a solid skirting board is described which is formed from a composite material consisting of particles in silicon coated with a polyester binder, to which a dye can be added. A disadvantage of this embodiment is that a smooth outer surface is difficult to achieve because of the particles in the mass. If a high gloss, good coloring and / or other additional properties are to be given to the skirting boards by means of additives, large amounts of these additives are required in this embodiment to obtain the desired result. Also, the properties of the core and of the surface cannot be influenced independently of each other.
    These skirting boards can therefore also be provided with a top layer on the outside that is intended to remain visible. This layer can also consist of plastic, because of its good chemical and water-repellent properties, to which a certain decorative effect can be given by means of a pigment. In order to increase the wear resistance of the skirting boards, a very strong cross-linking polymer resin is preferably also used for the top layer, such that ultimately a surface with high hardness is obtained.
    NL 1006957 describes a fender that is manufactured by first laying a prefabricated profile of fiber-reinforced synthetic resin in a preformed mold, or by making a top layer of a fiber-reinforced coating therein. That top layer is made from a coating that is safe for use in food, and that
    BE2019 / 5327 consists of polyester resin that is mixed and filled with fibers and / or glass fiber, manufactured to a certain impact strength. After the production of the top layer, the mold is filled with a composition consisting of very fine gravel parts, or other filling materials, and a polyester resin or another synthetic resin. Accessories such as inner and outer corners and end pieces are also described. NL 1006957 is not concerned with the compatibility between the binders of the top layer and the core, nor with the adhesion between the core and the top layer of the bumper.
    DE 3145334 A1 describes a step step which is manufactured by applying to a glass plate a thin layer of a mixture based on a resin "Feinschichtharz Nr. 325 ”, which has a gel time of eight to twelve minutes at an ambient temperature of 20 ° C, during which time the layer must be applied. About 20 minutes, at the latest two hours, after the thin layer has been applied to the glass plate, the material for the filling layer is then poured into the mold, which is based on a polyester resin, and then allowed to polymerize. The filler layer comprises 5 kg of polyester resin plus 1 liter (0.999 kg) of styrene as the curing resin components, together with 9 liters (9.9 kg) of quartz powder and 1 liter (1.3 kg) of quartz sand. This filling layer thus comprises 33.83% by weight of curing polymer in relation to the dry amount of filling composition. The inventors have also found that the adhesion between the core and the top layer of DE 3145334 A1 can be further improved.
    US 4346050 discloses a polymer-bonded concrete with low binder contents, which is proposed as building material for pre-cast panels for facade panels for buildings and for wall cladding. The concrete object can be given a plastic-like finish by applying a coating of pigmented resin in the mold before casting the concrete. The polymer concrete comprises at most 3.5% by weight of polyester resin plus styrene. Half or more of the polymer concrete in US 4346050 consisted of round quartz aggregates in the range of at least 1/8 "(3.18 mm) to 1/2" (12.7 mm) or even up to 1 "(25.4 mm). The average particle sizes of
    BE2019 / 5327 the round quartz aggregates used were therefore 8 mm or higher. Applicants have reproduced the product disclosed in US 4346050, and have found that the low curing resin content makes the composition very difficult to process, exhibits insufficiently low shrinkage making the product difficult to remove from the mold, and leads to a product that is too brittle for the main use as a skirting board of the present invention. In addition, the surfaces of the product obtained have an unacceptably high roughness. They do not meet the strict tolerances in terms of dimensions required for a connection with a narrow joint between adjacent skirting boards and an adhesion with a narrow joint to the wall. The products also do not meet the quality and aesthetics requirements imposed by the food industry.
    It is also not clear how such skirting boards with both a core and a top layer based on synthetic material can be manufactured in a simple manner. It is important that the top layer is attached to the material of the core as firmly as possible. From an aesthetic point of view, it is also desirable to obtain very smooth outer surfaces. Moreover, the top layer with its high hardness also entails a problem of a high brittleness, so that during mounting, which sometimes requires the use of a crowbar because of the weight of the element to be placed, there is a risk that chips will jump off the top layer and the aesthetic effect is thereby lost. Moreover, the brittleness of both the top layer and the core entails an additional problem that cracks can develop in the event of uneven shrinkage of the top layer and core, as a result of which the product can no longer be used as such and must often be disposed of as waste.
    A need therefore remains for a simple method for the manufacture of such covering elements, wherein the top layer has good adhesion to the core of the element, and also for skirting boards or other covering elements whose plastic top layer and / or the core is less brittle then what is known in the art so far.
    BE2019 / 5327
    In WO 2014/1149889 A1 a method is disclosed for the manufacture of a skirting board in which a stainless steel mold is first incorporated with a release agent, which is additionally incorporated. A gelcoat layer containing a polyester gelcoat and an initiator is then applied to the buried mold, and the coated mold is stored at 20 ° C for 20 minutes to partially cure the gelcoat layer, after which the mold is filled with a fill composition containing a solid mixture contains quartz grains, quartz sand and dolomite powder, mixed in a weight ratio of 79/21 with a binder of unsaturated polyester resin that further comprises 2% Andonox KP-LE from Syrgis Performance Initiators AB (SE) as a curing agent, plus 2% Accelerator NL-49P from Akzo Nobel Polymer Chemicals BV (NL). The Andonox KP-LE as a curing agent or catalyst comprises a mixture of two curing agents, namely methyl ethyl ketone peroxide as the faster curing agent and cumyl hydroperoxide as the slower curing agent, in dimethyl phthalate as a carrier. The core was filled and vibrated and allowed to further react and cure by storage for about 2 hours before the skirting product could be removed from the mold.
    A problem remains with regard to shortening the curing time of the final product. Other problems that can be addressed are the large amount of resin used in the art to manufacture the core fill composition, reuse of the molds, gelcoat layer and core adhesion, and the risk of deformation during curing of the core. final product.
    The present invention has for its object to solve or at least alleviate the problems described above, and / or to provide improvements in general.
    SUMMARY OF THE INVENTION
    According to the invention, a method is provided as defined in any of the appended claims.
    BE2019 / 5327
    In one embodiment, the invention provides a method for manufacturing an article for covering floors or walls, which comprises the following steps, performed in a mold:
    a) optionally applying a gelcoat layer, based on a first curing polymer resin, to the inside of the mold to obtain a coated mold,
    b) introducing into the core of the mold or into the core of the coated mold from step a) a fill composition based on a second curing polymer resin, supplemented with at least one mineral fill material, characterized in that the core of the mold article has a thickness of at least 10 mm, the core fill composition contains at least 5 weight% and at most 20 weight% curing polymer resin, relative to the dry amount of fill composition, and the fill composition contains only a single initiator in a concentration from 0.5% by weight to 5.0% by weight, relative to the amount of curing polymer resin in the fill composition.
    We have found that, for thick objects made of concrete with unsaturated polyester, and contrary to the prevailing prior art view of initiators for unsaturated polyester resins, it is advantageous to use only a single initiator in combination with a smaller amount of reactive resin.
    In the unsaturated polyester resin technique, the idea prevails today that objects of considerable thickness should use a combination of two initiators or curing agents, in particular one fast initiator and one slower initiator, to limit the exothermic character of the curing reaction. That advice was mainly prompted by the risk of discoloration of the product. However, we have found that the slow cure allows layer formation in the composition before the cure reaction is sufficiently advanced, and also necessitates the curing product to be in the mold for a long time
    BE2019 / 5327 remains. The formation of layers in the composition, whereby higher density components such as parts of the filling material can settle under the influence of gravity, can lead to a deformation of the product when it is released from the mold, whereby these products are useless and must be discarded. .
    We have found that by combining a smaller amount of curing polymer and a single initiator in the fill composition in a thick object, curing can be made much faster while the temperature during curing remains within its permissible limits. We have found that the peak temperature in those circumstances still remains acceptably low, but that the curing time can be considerably shortened. Moreover, the risk of product deformation is considerably reduced.
    Applicants have also found that the present invention also has the advantage that the temperature rises faster at the start of the core curing, and that the peak temperature in the core is also higher. Applicants have found that the higher peak temperature during curing of the core does not cause a problem of discoloration. The sharper and higher temperature profile during curing of the core entails the advantage that, if styrene is present in the fill composition, the concentration of styrene monomer remaining in the final product is lowered. This styrene monomer can be released from the product, especially when the product has to be cut or sawn to adjust its size to the available space. The present invention thereby brings with it an advantage in the field of industrial hygiene for the people who install the product. The reduced possible release of styrene is also of great importance in the food industry, since some foods tend to absorb styrene and can become inedible quickly due to a too high styrene content.
    The applicants have further noted that the reduced presence of reactive polymer in the fill composition
    BE2019 / 5327 improves the behavior of the final product in the event of fire, and that this improvement is noticeable in the results of fire tests according to international standards.
    Applicants have found that the fill composition must also meet the prescribed lower limit for the curing polymer content. Applicants have found that this condition is important to obtain a number of technical benefits. The higher curing polymer content makes it easier to mix the fill composition, to obtain a more homogeneous mixture, to prevent warping of the final product, and to allow the composition to pass through the equipment more smoothly. Another advantage is that the composition in the mold is easier to finish, and makes it possible to obtain tight dimensional tolerances, making the products suitable for narrow joint adhesives to attach the rear of the object to another surface, and for narrow joint bonding between adjacent objects adhered to the same surface. This also makes it easier to meet the requirements for finishing surfaces of the food industry. Another advantage is that the higher curing polymer content also entails a stronger shrinkage during curing, such that the finished product can easily be taken out of the mold.
    Applicants have found that the article as manufactured by the method according to the present invention comprising step a) is very suitable in so-called "High Care" applications, such as in the more sensitive areas of buildings in which pharmaceutical products are produced on an industrial scale. are produced, or in the food industry where foods are prepared and packaged. Applicants have found that the article as manufactured by the method of the present invention that does not include step a) is very acceptable in so-called "Low Care" applications, where the requirements in the field of industrial hygiene are less strict.
    DETAILED DESCRIPTION
    The present invention will become hereafter
    BE2019 / 5327 described in specific embodiments and with possible reference to certain illustrations; however, it is not limited to that, but is only determined by the conclusions. The illustrations described are only schematic and non-limiting. In the drawings, the size of some elements for illustrative purposes may be magnified and not drawn to scale. The dimensions and relative dimensions in the drawings do not necessarily correspond to actual practical embodiments of the invention.
    Furthermore, the terms first, second, third, and the like, in the description and claims, are used to distinguish between similar elements, and not necessarily to describe a sequential or chronological order. The terms are interchangeable under appropriate conditions, and the embodiments of the invention may function in sequences other than described and / or illustrated herein.
    Furthermore, the terms upper, lower, top, bottom, and the like, in the description and the claims, are used for descriptive purposes, and not necessarily to describe relative positions. The terms thus used are interchangeable under appropriate circumstances, and the embodiments of the invention described herein may function in orientations other than described or illustrated herein.
    The term "comprising", as used in the claims, should not be interpreted as being limited to the resources listed in its context. He does not exclude that there are other elements or steps. The term is to be interpreted in the sense that it indicates the presence of said properties, numbers, steps or components as indicated, but does not exclude the presence or addition of one or more other properties, numbers, steps or components, or groups thereof from. The scope of the expression "an object comprising resources A and B" is therefore not necessarily limited to an object composed only of resources A and B. It means that A and B are the only elements of importance for what is discussed in bandage
    BE2019 / 5327 with the present invention. In that sense, the terms "include" or "contents" also include the more restrictive terms "consisting essentially of" and "consisting of". Thus, by replacing "include" or "contents" with "consist of", these terms form the basis of preferred but narrowed embodiments which are mentioned as part of the contents of this document in connection with the present invention.
    Unless otherwise stated, all values specified herein include the range up to the indicated end points, and the values of the components or components of the compositions are expressed in percent by weight or% by weight of each ingredient in the composition.
    The terms "weight percent," "weight%," "percent by weight," "% by weight,", "ppm by weight", "ppm by weight", "weight ppm" or "ppm" and variations thereof such as they are used in this document refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100 unless otherwise indicated. The reader should assume that "percent" and "%" in this document are used as synonyms for "weight percent," "weight percent," etc.
    Note that, in this description and in the appended claims, the singular forms "one," "the" and "it" may also refer to multiple things unless the content clearly indicates otherwise. For example, a reference to a composition containing "a compound" also includes a composition with two or more compounds. Also note that the term "or" is generally used in the sense that also includes "and / or" unless the content clearly states otherwise.
    Furthermore, each compound in this document can be discussed interchangeably by its chemical formula, chemical name, abbreviation, etc.
    In one embodiment of the present invention, the fill composition comprises the one initiator or the curing agent or the catalyst in a concentration of at least 1.0 weight% relative to the amount of curing polymer resin in the
    BE2019 / 5327 filling composition, preferably at least 1.25% by weight. Applicants have found that this contributes to the desired cure speed and to the properties of the final product. Optionally, the fill composition contains at most 4.50% by weight of the initiator, preferably at most 4.0% by weight, more preferably at most 3.5% by weight, even more preferably at most 3.0% by weight %, preferably at most
    2.5% by weight, more preferably at most 2.0% by weight, even more preferably at most 1.5% by weight. The applicants have found that it is not necessary to exceed the indicated upper limit, because even more initiator does not provide sufficient benefits to justify the larger quantity.
    In an embodiment of the present invention, the core of the article has a thickness of at least 15 mm, preferably at least 20 mm, more preferably at least 25 mm, even more preferably at least 30 mm. Applicants have found that the advantages of the present invention become even more pronounced when the core of the article has a greater thickness. Optionally, the core of the article has a thickness of at most 200 mm, preferably at most 175 mm, more preferably at most 150 mm, even more preferably at most 125 mm, preferably at most 100 mm, more preferably at least at most 80 mm, even more preferably at most 60 mm. Applicants have found that it is advantageous to limit the thickness of the core as indicated, because an even greater thickness does not yield many additional mechanical properties, but does increase the weight and amount of material used in the article, leading to higher costs for the material. production and processing of the article.
    In an embodiment of the present invention, the core is fiber-reinforced. The applicants particularly prefer to reinforce thinner products with a fiber layer. Applicants preferably use fiberglass for reinforcement. Applicants preferably apply the fiber reinforcement to the top of the core after the filler composition has been introduced and leveled.
    BE2019 / 5327
    In one embodiment of the present invention, the core fill composition contains at most 19% by weight of curing polymer resin, preferably at most 18% by weight, more preferably at most 17% by weight, even more preferably at most 16% by weight %, preferably at most 15% by weight, more preferably at most 14% by weight, even more preferably at most 13% by weight, preferably at most 12% by weight, more preferably at most 11% by weight even more preferably at most 10% by weight of the second curing resin. Applicants have found that the lower the curing polymer resin concentration in the fill composition, the sharper the temperature profile may be during curing, and the more active the selected curing agent may be.
    Optionally, the fill composition contains at least 5.0% by weight of the second curing resin, preferably at least 6% by weight, more preferably at least 7% by weight, even more preferably at least 8% by weight, preferably at least 9% by weight, more preferably at least 10% by weight, even more preferably at least 11% by weight of the second curing resin. Applicants have found that the higher the concentration of the second curing resin in the fill composition, the better the mechanical properties of the core.
    In principle, a wide variety of thermosets or heat-curing polymers or polymer resins can be used in the context of the present invention. Alkyd resins, phenol-formaldehyde resins (PF resins), diallyl phthalate resins (DAP resins), melamine-formaldehyde resins (MF resins), polyester resins and urea-formaldehyde resins (UF resins) are possible.
    However, the inventors prefer to use unsaturated polyesters, because these resins absorb virtually no moisture and may even be water-repellent, resistant to cold and heat, resistant to acids, oxidizing agents and diluted bases, resistant to sunlight, be very durable, extremely pressure resistant, can be highly glossy, and do not suffer from
    BE2019 / 5327 bacteria and fungi. Moreover, they are easy to process, the curing reaction is easy to start up and the reaction speed is easy to control, all in an easily reachable temperature range that usually includes the normal ambient temperature and / or room temperature. The inventors have also found that the curbs based on cured polyester have an impact resistance that is twice as high as that of concrete. An additional advantage is that these polyesters also undergo a small shrinkage during curing, which makes it much easier to take the products out of shape.
    In an embodiment of the present invention, the second curing polymer belongs to the family of unsaturated polyester polymer resins, and a vinyl monomer, more preferably styrene, is preferably admixed for the curing reaction.
    In the core fill composition applied in step b), the applicants preferably use a composition that is also based on unsaturated polyester resin as a binder, together with at least one mineral fill material.
    Unsaturated polyesters are curing polymer resins. In general, they are copolymers obtained by polymerizing one or more polyols, usually diols, such as monoethylene glycol (MEG), with unsaturated dicarboxylic acids such as maleic or fumaric acid, and / or the anhydrides thereof. Partially saturated and / or aromatic acids and / or their anhydrides can also be used herein, such as the various forms of phthalic acid or phthalic anhydride. The double bond of the unsaturated polyesters reacts during curing with a vinyl monomer, usually styrene, such that a three-dimensional cross-linked structure is formed. Cross-linking is usually initiated by an exothermic reaction in which an organic peroxide can be used as the initiator, which is also often, less accurately, referred to as the catalyst, such as methyl ethyl ketone peroxide, benzoyl peroxide or dibenzoyl peroxide. The initiator usually works by releasing a free radical that initiates the polymerization or chain reaction.
    BE2019 / 5327
    As the vinyl monomer, styrene, α-methyl styrene, para or meta-styrene, divinyl benzene, diallyl phthalate and prepolymers thereof, diallyl isophthalate, diallyl terephthalate or prepolymers thereof, N-vinyl pyrrolidone, triallyl cyanurate, diallyl melamine or the like are used alone or in mixtures with each other. Other vinyl monomers that can be used are the alkyl styrenes, and other allyl, acrylate or methacrylate esters.
    Suitable unsaturated polyesters are offered commercially by many companies and are available with a wide variety of properties. Such polyesters are also commercially available in blends with styrene such that they can be used immediately as a binder in step b) of the process of the present invention.
    In one embodiment of the present invention, the one initiator in the fill composition is an organic peroxide, more preferably methyl ethyl ketone peroxide (MEKP).
    The cross-linking or curing reaction with unsaturated polyester resins is preferably a free radical polymerization reaction. That reaction is preferably started by an initiator, which is also called curing agent, curing agent or catalyst. Peroxides are preferably used as the initiator for the curing reaction, often a combination of several peroxides, more preferably organic peroxides because they are less volatile, and because they can often be supplied as a liquid. Suitable are, for example, hydrogen peroxide, benzoyl peroxide, lauryl peroxide, dicumyl peroxide, p-tertiary butyl perbenzoate, acetylacetone peroxide (AAP), methyl isobutyl ketone peroxide and the like. Applicants preferably use methyl ethyl ketone peroxide (MEKP). MEKP delivers reliable performance at ambient temperature and at room temperature. The MEKP is normally supplied as a solution of 30-40% by weight in a suitable solvent, such as, for example, dimethyl phthalate ester. In addition, a phlegmatizer is preferably added, a substance that stabilizes the relatively unstable peroxide during storage and for transport and processing until it serves its function
    BE2019 / 5327. As phlegmatizer, for example, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, also referred to as TXIB, can be used. Other organic compounds with little to none of the relatively less stable -CH 2 groups can also be used. The initiator brings with it the advantage that the crosslinking or curing reaction can be started at ambient and / or room temperature. This avoids extremely high temperatures, which can otherwise lead to discoloration in thin products or in top layers, and even to the deterioration of the chemical and mechanical properties of the product.
    Applicants preferably apply the curing agent at a concentration of 1.0-5.0% by weight relative to the total amount of resin, preferably 1.2-4.0% by weight, more preferably 1.4- 3.0% by weight, even more preferably 1.5-2.5% by weight, and even more preferably 1.8-2.2% by weight, typically about 2.0% by weight %, and that based on the weight of the total amount of resin, including the other monomers such as the vinyl monomer and / or DCPD, in the composition.
    In an embodiment of the present invention wherein the method comprises step a), the first and the second curing polymer resin belong to the same chemical family of curable polymer resins. Applicants have found that this improves the adhesion between the gel coat layer and the core.
    In an embodiment of the present invention wherein the method comprises step a), the gel-coated layer in the coated mold of step a) is only partially cured before the coated mold of step a) is subjected to step b).
    In an embodiment of the present invention wherein the method comprises step a), the curing polymer resin of step a) is cured only until the gelcoat layer is at most dry to touch before the coated cast of step a) is subjected to step b).
    We have found that the method according to the present invention is extremely simple, and that, moreover,
    BE2019 / 5327 if the method comprises step a), because the gelcoat layer is only partially cured before the filler composition is introduced into step b), preferably only until the gelcoat layer is at most dry to touch, without exceptionally good adhesion provides one layer of glue between the gel coating top layer and the core of the manufactured product. We have also found that through a well-considered selection of the base materials, and by adding and correctly selecting additives, initiators, reaction accelerators and / or retarders, the hardening course of the resins of step a) and of step b) is independent can be determined from each other in such a way that they optimally meet the prescribed requirements and at the same time can be adapted to each other in order to make it possible to manufacture a product with the desired properties, in a simple and fast manner and with relatively little intervention by people.
    In an embodiment of the present invention wherein the process comprises step a), the first curing polymer resin belongs to the family of unsaturated polyester polymer resins, and for the curing reaction, a vinyl monomer is preferably admixed, more preferably styrene.
    Unsaturated polyesters are curing polymer resins. In general, they are copolymers obtained by polymerizing one or more polyols, usually diols, such as monoethylene glycol (MEG), with unsaturated dicarboxylic acids such as maleic or fumaric acid, and / or the anhydrides thereof. Partially saturated and / or aromatic acids and / or their anhydrides can also be used herein, such as the various forms of phthalic acid or phthalic anhydride. The double bond of the unsaturated polyesters reacts during curing with a vinyl monomer, usually styrene, such that a three-dimensional cross-linked structure is formed. Cross-linking is usually initiated by an exothermic reaction in which an organic peroxide can be used as the initiator, which is also often, less accurately, referred to as the catalyst, such as methyl ethyl ketone peroxide, benzoyl peroxide or dibenzoyl peroxide. The initiator usually works by releasing a free radical that initiates the polymerization or chain reaction.
    BE2019 / 5327
    As the vinyl monomer, styrene, α-methyl styrene, para or meta-styrene, divinyl benzene, diallyl phthalate and prepolymers thereof, diallyl isophthalate, diallyl terephthalate or prepolymers thereof, N-vinyl pyrrolidone, triallyl cyanurate, diallyl melamine or the like are used alone or in mixtures with each other. Other vinyl monomers that can be used are the alkyl styrenes, and other allyl, acrylate or methacrylate esters.
    Suitable unsaturated polyesters are offered commercially by many companies and are available with a wide variety of properties. Such polyesters are also commercially available in blends with styrene such that they can be used immediately as a binder in step b) of the process of the present invention.
    The compositions of the method according to the present invention are preferably based on a polyester, for example obtained by the esterification of a polyvalent carboxylic acid with a polyol, i.e.: a chemical substance with at least two hydroxyl groups (OH groups).
    The polyvalent carboxylic acid of the polyester resin can be aliphatic or aromatic. Applicants preferably use a polyester formed on the basis of an aromatic polyvalent carboxylic acid. Suitable candidates are, for example, phthalic acid, also known as orthophthalic acid, isophthalic acid and / or terephthalic acid, but acids with several benzene nuclei are also possible. Applicants prefer a gelcoat based on orthophthalic acid, most preferably based primarily on orthophthalic acid.
    There are many polyols that can be used in the polyester of the present invention. Suitable are, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, and bis (β-hydroxypropyl) ether of bisphenol A. Applicants prefer a polyol that has only two hydroxyl functions per molecule. Suitable candidates are available in large quantities,
    BE2019 / 5327 such as ethylene glycol, monoethylene glycol, ethylene glycol oligomers such as diethylene glycol, triethylene glycol, and tetraethylene glycol, 1,2-propanediol, 1,3-propanediol or oligomers thereof, such as dipropylene glycol and other polypropylene glycols, 1,2-butanediol 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-octanediol, 1,3-butanediol, 1,2-pentanediol, 2-methyl-2,4-pentanediol, neopentyl glycol, bisphenol A, the bis- (β-hydroxypropyl) ether of bisphenol A, and others.
    Together with a divalent carboxylic acid, a divalent polyol produces a so-called "linear" polyester. This avoids excessive cross-linking, such that the viscosity of the polyester is kept relatively low, such that the substance containing the polyester is sufficiently spreadable or sprayable, or flows easily enough before the curing step, such that a good adaptation to the casting mold, or a good filling of the available space can be realized quickly, with minimal effort. Applicants prefer a gelcoat based primarily on a resin made from substantially pure isophthalic acid together with neopentyl glycol.
    In the preparation of the unsaturated polyester, unsaturated carboxylic acids are often used. Ethylene-like α, β-unsaturated dicarboxylic acids, for example maleic acid, fumaric acid, citraconic acid, itaconic acid, mesaconic acid and the like, or the anhydrides thereof are suitable.
    In the production of the unsaturated polyester, often saturated carboxylic acids are also used. Suitable are (ortho) phthalic acid or its anhydride, tetrahydrophthalic acid (or its anhydride), hexahydrophthalic acid (or its anhydride), isophthalic acid, terephthalic acid, adipic acid and succinic acid or dihydric butanoic acid.
    As chain terminators, monohydric alcohols or acids can be used in the manufacture of the polyester monomers that can be used as base materials in the present invention. In addition, these components can be used straight-chain or branched. Also useful are polyhydric alcohols, such as
    BE2019 / 5327 glycerin, trimethylolpropane, pentaerythritol or the like, for, where possible, already causing some cross-linking in the monomer.
    The polyesters are often presented as a solution in a liquid vinyl monomer, preferably styrene. The formulation is then diluted, or "modified", by the addition of dicyclopentadiene (DCPD). This DCPD provides additional crosslinking of the final cured polymer, and because the reagent is a liquid, it provides the possibility to use less styrene to achieve the same low viscosity for the gelcoat, to allow proper processing. For the gelcoat, therefore, applicants sometimes prefer a "pre-accelerated" version of this gelcoat, in which an amount of catalyst is added to achieve a faster curing reaction. As a catalyst, methyl ethyl ketone peroxide (MEKP) is preferably used, but other peroxides, such as acetyl acetone peroxide (AAP), are also suitable. Prior to curing, this gelcoat preferably has a viscosity of from 2000 to 30,000, preferably from 5,000 to 25,000, more preferably from 8,000 to 20000, and most preferably from 10,000 to 18,000 millipascal seconds (mPa.s) or centipoise (cPs) at 20 ° C, measured according to NFT 51 210, with a Brookfield RVF 100 meter, using a spindle No. 5 at 20 revolutions per minute. Suitable versions are available as gelcoat HPH 6098 ST Paraf. at Ferro Plastics Europe, but also as a polyester gel coat GC 875 9270 at Nord Composites.
    In an embodiment of the present invention wherein the method comprises step a), the first curing polymer resin has a gel time of at least 10 minutes, preferably at least 11 minutes, and optionally at most 20 minutes, preferably at most 18 minutes, with more preferably at most 16 minutes. Applicants have found that a curing polymer resin selected in this way causes the full curing to take place more slowly, thereby improving the adhesion between the core and the gel coat layer while maintaining the desired property that the gel coat is retained. are applied to the mold, it quickly becomes dry when touched (“touch
    BE2019 / 5327 dry ”), even within 40 minutes, and then ready to receive the fill composition in the mold.
    Applicants preferably use a gelcoat available from Polyprocess (FR), polyester gelcoat Iso / NPG, type GCIG Series W-VM, which has a gel time in the range of 1116 minutes.
    The cross-linking or curing reaction with unsaturated polyester resins is preferably a free radical polymerization reaction. That reaction is preferably started by an initiator, which is also called curing agent, curing agent or catalyst. Peroxides are preferably used as the initiator for the curing reaction, often a combination of several peroxides, more preferably organic peroxides because they are less volatile, and because they can often be supplied as a liquid. Suitable are, for example, hydrogen peroxide, benzoyl peroxide, lauryl peroxide, dicumyl peroxide, p-tertiary butyl perbenzoate, acetylacetone peroxide (AAP), methyl isobutyl ketone peroxide and the like. Applicants preferably use methyl ethyl ketone peroxide (MEKP). MEKP delivers reliable performance at ambient temperature and at room temperature. The MEKP is normally supplied as a solution of 30-40% by weight in a suitable solvent, such as, for example, dimethyl phthalate ester. In addition, a phlegmatizer is preferably added, a substance that stabilizes the relatively unstable peroxide during storage and before transport and processing until it has to perform its function. As phlegmatizer, for example, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, also called TXIB, may be used. Other organic compounds with little to none of the relatively less stable -CH 2 groups can also be used. The initiator entails the advantage that the crosslinking or curing reaction can be started at ambient and / or room temperature. As a result, extremely high temperatures are avoided, which could otherwise lead to discoloration, and even to the deterioration of the chemical and mechanical properties of the product.
    BE2019 / 5327
    In an embodiment of the present invention wherein the method comprises step a), the gel coat layer in step a) comprises at least one initiator, preferably only one initiator, preferably an organic peroxide, more preferably methyl ethyl ketone peroxide (MEKP). Applicants have found that the initiator brings with it the advantage that the temperature window in which the hardening of the gelcoat can start, becomes wider, and can be brought to the extent that it comprises room temperature. The selection of MEKP further contributes to the creation of the quick partially cured gelcoat in the mold, which is preferably touch-dried, such that the mold can be subjected to step b) relatively quickly, while still retaining the desired property of a slower full cure of the gelcoat, as set forth above.
    Applicants preferably use a high concentration of gelcoat in the gelcoat layer, such as at least 60% by weight based on the total gelcoat layer, preferably at least 70% by weight, even more preferably at least 80% by weight , preferably at least 90% by weight, more preferably at least 95% by weight, even more preferably at least 98% by weight. Applicants preferably use no or very little filler materials in the gelcoat layer, because a smoother outer surface of the coating element is thereby obtained. Preferably, the applicants add a pigment to the gelcoat layer.
    Applicants in the gel coat layer preferably also provide a curing agent or initiator, as set forth above. Preferably, the applicants prefer to use the methyl ethyl ketone peroxide as the sole curing agent. This curing agent is preferably used as a solution of 30-40% by weight in 40-50% by weight of dimethyl phthalate, together with a solution of 10-20% TXIB as a phlegmatizer or stabilizer. A suitable curing agent solution is, for example, available as Andonox KP-100 from Norac ANDOS AB, Norpol Peroxide 1, which is available from United Initiators (DE), and Butanox M-50, which is available from Akzo Nobel Functional Chemicals (NL) ). Curing agent concentrations given in this document are intended as the concentrations of the
    BE2019 / 5327 curing agent solution, including the solvent and the stabilizer, and any other components of the solution.
    Applicants preferably apply the curing agent in a concentration of 1.0-5.0% by weight of the gelcoat layer, preferably 1.2-4.0% by weight, more preferably 1.4-3.0% in weight, even more preferably 1.5-2.5% in weight, and even more preferably 1.8-
    2.2% by weight, typically 2.0% by weight, and that based on the weight of the total amount of resin, including the other monomers such as the vinyl monomer and / or DCPD, in the gelcoat layer .
    In an embodiment of the present invention, the core fill composition in step b), and / or, if step a) is present, the gel coat layer in step a) further comprises an accelerator for the curing reaction, preferably an organometallic compound, more preferably an organic cobalt salt, even more preferably cobalt octanoate.
    An accelerator is often used to speed up the curing reaction. Suitable are, for example, the salts of cobalt, manganese, vanadium and iron, beta-diketones selected from derivatives of acetylacetone, derivatives of acetoacetamide, and esters of acetoacetic acid, but also tertiary aromatic amines such as, for example, dimethylaniline, dimethyl-p-toluene , diethylaniline, phenyl diethylaniline, phenyldiethanolamine and the like. They are typically used in concentrations of 0.05-1.0 parts by weight per hundred parts of resin. Metal components are therefore usually only meant to mean the concentration of the metal.
    As a reaction accelerator or accelerator, applicants preferably use cobalt, more preferably a cobalt compound, more preferably an organometallic cobalt compound. Cobalt octanoate, which contains cobalt at 6% by weight and is effective in small amounts, such as 0.10-0.30% by weight, preferably 0.15-0.20% by weight, is particularly suitable. the resin. Applicants have found that this accelerator is very suitable at these concentrations, along with 1.0-3.0% by weight MEKP initiator, preferably 1.5-2.5% by weight MEKP.
    Applicants preferably use a high concentration of gelcoat in the gelcoat layer, such as at least 60% by weight
    BE2019 / 5327 based on the total gelcoat layer, preferably at least 70% by weight, even more preferably at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight. %, even more preferably at least 98% by weight. Applicants preferably use no or very little filler materials in the gelcoat layer, because a smoother outer surface of the coating element is thereby obtained. Preferably, the applicants add a pigment to the gelcoat layer.
    In an embodiment of the present invention wherein the method comprises step a), the gel coat layer contains a suitable amount of titanium dioxide as a pigment. The titanium dioxide acts as a pigment, but also acts as a filler. In addition, the titanium dioxide performs an antibacterial function, presumably but not necessarily due to the rejection of bacteria, which is highly appreciated in sensitive applications, inter alia in the food industry.
    In the core fill composition in step b), the applicants preferably use a substantial amount of fill material. This imparts important mechanical properties to the core, and is also more readily available than the binder, such that the products of the process of the present invention can be supplied for many applications, thereby offering an economically valuable alternative as compared to other products that manufactured on a different basis.
    A wide variety of potential candidates can be considered suitable as filling material. In principle, all solids to which the binder wants to attach can be used as granules, including recycled plastics.
    However, the applicants preferably use at least partially mineral filler material, most preferably only mineral filler material, primarily because it is chemically less active, usually even inert, and therefore has no influence on the crosslinking of the filler material and / or the curing reaction. In addition, mineral filler materials usually have a lower porosity than, for example, plastics, so that they absorb less and the binder
    BE2019 / 5327 amount of resin does not have to be increased to compensate for that absorption. An additional advantage is the generally wide availability of suitable mineral filling materials.
    In an embodiment of the present invention, the mineral filler material in step b) is selected from the list consisting of quartz, preferably quartz grains, more preferably quartz grains with an average particle size in the range of 1 to 3 mm, more preferably dried quartz grains, sand, preferably sand that has been dried and sieved, dolomite powder, and mixtures or combinations thereof.
    Applicants prefer a mineral filler material whose particles are obtained by breaking, rather than round aggregates. The applicants have found that this results in a better bond between the curing resin and the padding material at the corners of the product.
    Applicants have found that a combination of a first filler material comprising larger grains and a second filler material with a finer grain size provides a very good degree of fill, and yet makes it possible to limit the amount of polymer resin required as a binder. Applicants prefer that the smaller grains are selected so that they fit into the spaces of a stack of the larger grains, such that they at least partially fill the spaces between the large grains with filler material, thereby requiring less binder material is. Therefore, applicants preferably use a mixture of a first filler material with granules having an average diameter in the range of 0.5-5 mm, preferably at least 1.0 mm, and also preferably not more than 4 mm, with more preferably no more than 3 mm, with a second filler material with fine grains having an average diameter in the range of 50-500 μm, preferably 100-400 μm, more preferably 150350 μm, more preferably 200-300 μm and even more preferably, at 235280 μm.
    Applicants preferably use a mixture comprising 56 parts by weight of quartz grains with an average
    BE2019 / 5327 particle diameter in the range of 1 to 3 mm, and 32 parts by weight of quartz sand with an average particle diameter (D50) of approximately 260 μm.
    Many suitable candidates are available as the first filling material. Applicants preferably use EIFEL quartz, 1-3 mm, which is available from EUROTREX or EIFEL QUARTERS 1/3 from E.VICTOR-MEYER (BE). As a second filling material, a whole range of suitable candidates is also available. Applicants preferably use M32 quartz sand, which is available from SIBELCO Benelux (BE).
    The applicants have found that the filling properties of the filling material can be further improved by adding a third filling material with an even smaller grain size, which is also suitable for filling in the smaller spaces between the grains of the second filling material. The inventors prefer that the third filler material has an average grain diameter (D50) in the range of 5-200 μm, preferably 10-100 μm, more preferably 20-70 μm and even more preferably 30-50 μm . There are many suitable fillers available. Applicants therefore preferentially use dolomite, which consists of about 99% by weight of calcium magnesium carbonate CaMg (CO3) 2, such as dolomite powder Microdol A 70 available from OMYA Benelux. This powder also has the advantage that it also acts as a pigment and makes the color of the composition lighter, which is beneficial to have no effect on the color that contributes to the gel coat layer.
    Applicants preferably use a mixture of about 56 parts of dried silica 1-3 (e.g. 1-3-EIFEL quartz) with about 33 parts of treated sand (e.g. M32 SIBELCO quartz sand) in which further about 11 parts of dolomite powder (e.g. Microdol A70 from OMYA or Madol 100 from E.VICTOR-MEYER).
    In an embodiment of the present invention wherein a mineral filler material is used comprising dolomite powder, the dolomite powder has a pH of at most 9.5, preferably at most 9.0, more preferably at most 8.5, with still
    BE2019 / 5327 more preferably at most 8.0, preferably at most 7.5, more preferably at most 7.0, more preferably at most 6.5, and optionally at least 5.5, preferably at least 6 , 0. Applicants have found that bringing the pH of the dolomite powder within the prescribed limits entails the advantage that the dolomite powder absorbs less resin, such that more resin remains available as a binder for the composition. Applicants have found that this property of the dolomite powder made it possible to reduce the amount of binder in the composition in order to obtain the same final product properties. Applicants have found that this property made it possible to significantly reduce the concentration of the binder in the fill composition. Applicants preferably use Madol 100 dolomite powder, available from E.VICTOR-MEYER (BE), which has a pH of 6.38.
    In one embodiment of the present invention, the mold before step b), or if the method comprises step a) prior to applying the gel coat layer in step a), is treated with a release agent.
    To make it easier to remove the product from the mold, after the possible hardening of the gelcoat layer and the hardening of the composition in the core, the inventors prefer that the mold is lubricated with an external release agent or a release wax (also " mold release agent "or" mold release wax "). In one embodiment of the method according to the present invention, the mold, before step b) or before applying the gelcoat layer in step a), is lubricated with a release agent (mold release agent, release wax). This release wax is preferably incorporated into the mold because it provides a smoother outer surface of the manufactured article, which increases the aesthetic appearance but also the hygienic aspect of the article.
    Many substances and compositions are suitable as a release agent. Applicants prefer to use silicone-free compositions to prevent unwanted color effects on the cured
    BE2019 / 5327 gelcoat layer. Versions with little or no color of their own, preferably transparent and a color of at most 6 Gardner (ASTM D 1544-80), and even better at most 4 Gardner, are better because they do not substantially influence the color of the product. Applicants preferably use hydrocarbon mixture, or a derivative thereof. Very suitable are, for example, hydrogenated petroleum distillates, preferably the heavier fractions with a boiling point of at least 140 ° C, and preferably also a flash point (closed vessel) of at least 24 ° C. These heavier fractions set fewer requirements with regard to industrial hygiene and safety. Nevertheless, we prefer to use fractions that are not too heavy, at least partially, preferably the middle distillate fractions, also known as kerosene or diesel oil types. Heavier fractions, such as washing, can then be dissolved therein. Even more suitable are fractions that are also desulfurized to a low sulfur content, such as at most 50 ppm by weight, preferably at most 30 ppm by weight, and even more preferably at most 10 ppm by weight. As a result, they also offer a higher chemical resistance, and a higher resistance to discoloration, usually yellowing, and are also suitable for contact with food. Suitable products are, for example, Ce-Sense Slip-X10, which is available from Brands Structural Products (NL).
    The release agent can be applied by hand or by syringe. Preferably, the release agent is allowed to dry before polishing to a high gloss. On new or cleaned molds, the material is preferably applied 2-3 times thinly in order to obtain good coverage and an even thickness.
    Applicants prefer that this external release agent is applied in a very homogeneous thin layer with a very smooth upper surface. This ensures that the upper surfaces of the product of the process that have been in contact with a wall of the mold, get a very smooth appearance, and even become shiny.
    In addition, an internal release agent can also be used. Many materials are suitable for this. The applicants
    BE2019 / 5327 prefers ADDITIV MIKON® INT-250 from MUNCH-CHEMIE to be used as an additional ingredient in the gelcoat layer.
    In an embodiment of the present invention, the release agent comprises a polymer resin, preferably dissolved in an aliphatic hydrocarbon solvent. Applicants preferably use as the release agent the product available from Marbocote Ltd (UK) under the brand name and type SPRAYCOTE FD. Applicants have found that this type of release agent has several advantages. It is semi-permanent in the sense that the mold in which this type of release agent is applied can be reused more than three times before a new layer of release agent must be applied. The applicants have furthermore found that the mold does not need to be cleaned before the next layer of release agent can be applied, which was necessary with other types of release agents to remove contaminants that would lead to dull and / or rough surfaces and rejected products. These advantages lead to a significant reduction in the amount of human intervention required by the method of the present invention. The applicants have furthermore found that this type of release agent leads to a better gloss and surface smoothness of the final product, elements that strongly contribute to better aesthetic characteristics and the impression of a higher quality.
    In an embodiment of the present invention wherein the method comprises step a), the gel coat layer is applied by a technique selected from the list of smears, for example with a brush and / or a roller, spraying, and combinations thereof, at preferably by spraying with a spray gun under pressure.
    In an embodiment of the present invention, the polymer resin of the core and / or of the gelcoat layer, also called the top layer, is added with at least 0.5% and at most 20% by weight, expressed on the basis of the total amount of polymer resin in the top layer or in the core, of an additional unsaturated polyester resin that is characterized by an elongation at break after curing the resin, tested according to ISO 527, of at least 4.0%.
    BE2019 / 5327
    Preferably the elongation at break of this additional unsaturated polyester resin, after curing the resin, tested according to ISO 527, is at least 5.0%, more preferably at least 10%, even more preferably at least 20%, at preferably at least 30%, more preferably at least 40%, and even more preferably at least 45%. If necessary, this resin can be selected such that the elongation at break is no more than 100%, preferably no more than 75%, and more preferably no more than 60%. In this way the risk is reduced that the hardness would decrease.
    The resin is usually obtained by making the polyester chain slightly longer, preferably by incorporating longer polyol monomers, preferably polyol monomers, the chains of which are not strictly linear, but which have angles. For example, instead of monoethylene glycol alone, oligomers thereof may also be used, preferably oligomers containing one or more ether functions as part of the chain. For example, triethylene glycol or tetraethylene glycol can be used in the manufacture of these polyesters. It is also possible to start with a mixture of polybasic carboxylic acids, or to produce polyesters with longer chain lengths, in order to obtain a polyester that will form fewer crystalline and more amorphous zones, such that the cured resin will show a certain degree of elasticity.
    The inventors prefer not to use more than 15% by weight of this additional polyester resin for the core, in the first place because the hardness of the final product may not decrease too strongly. More preferably, the inventors use a maximum of 10% by weight, even more preferably a maximum of 5% by weight, and even more preferably a maximum of 3% by weight of this additional resin, relative to the total amount of resin used in the core filling composition.
    In the gelcoat layer, the inventors preferably use no more than 16% by weight of this additional polyester resin. More preferably, the inventors use at most 12% by weight, even more preferably at most 9% by weight, and even more preferably at least
    BE2019 / 5327 maximum 7% by weight of this additional resin, relative to the total amount of resin used in the gelcoat layer fill composition. The inventors preferably use at least 2% by weight in the gelcoat layer, more preferably at least 3% by weight and even more preferably at least 4% by weight, expressed on the same basis. This amount appears to be sufficient to give the gel coating top layer the desired properties. As will be explained later, this additional resin can also be used in a pre-mixed manner.
    The inventors have found that this additive gives the cured gel coat layer and / or the cured core a greater elasticity. This provides various benefits. When it is added to the core, the advantage is that fewer residual stresses occur, which may arise from differences in shrinkage in the core itself due to possible local differences in composition, but also between the core and the gelcoat layer. The stresses are reduced, and lead to cracks less easily, so that far fewer end products have to be rejected or treated in order to be usable.
    The addition of the additional polyester resin also has the advantage that when placing the covering element, which can have a considerable weight depending on its size and therefore must often be placed with the aid of mechanical aids such as a crowbar, there is less risk of peeling off the gelcoat layer, so that the aesthetic effect is better preserved, and fewer elements become unusable during installation and must be replaced and / or discarded.
    In one embodiment of the present invention, the fill composition further comprises a substance selected from a dye, a pigment, paint flakes, metal flakes, and combinations thereof. The gelcoat layer can thus be pigmented with a wide selection of pigments, in any available color, for example with any of the available RAL colors. Applicants have found that the article produced by the method of the present invention can be made aesthetically more attractive without step a), which
    BE2019 / 5327 makes the object more acceptable for many applications. Applicants preferably use a pigment, preferably a white pigment, in a concentration of at least 0.05% by weight and at most 2.0% by weight relative to the total weight of the fill composition, preferably at least 0 , 1% by weight, more preferably at least 0.2% by weight, even more preferably at least 0.3% by weight and optionally at most
    1.5% by weight, preferably at most 1.0% by weight, more preferably at most 0.6% by weight, even more preferably at most 0.5% by weight on the same basis. Applicants have found that by adding this pigment, the viscosity of the fill composition is also reduced, so that it is easier to process and the produced article gets smooth surfaces more easily.
    In an embodiment of the present invention wherein the method comprises step a), the gel coat layer further comprises a substance selected from a dye, a pigment, a filler, paint flakes, metal flakes, and combinations thereof. The gelcoat layer can thus be pigmented with a wide selection of pigments, in any available color, for example with any of the available RAL colors. A transparent version may also be possible without the addition of a colorant.
    In an embodiment of the present invention wherein the method comprises step a), partially curing the gelcoat layer comprises storing the coated mold in an environment with a temperature in the range of 10 ° C to 50 ° C, preferably at least 15 ° C and more preferably at least 18 ° C, and optionally no more than 35 ° C, preferably at most 30 ° C, even more preferably at most 25 ° C, and even more preferably at most 23 ° C. The storage preferably takes place over a period of at least 2 minutes, preferably at least 5 minutes, even more preferably at least 10 minutes, and even more preferably at least 15 minutes. The storage optionally lasts no longer than 24 hours, preferably no longer than 18 hours, more preferably no longer than 12 hours, and even more preferably no more than 6 hours.
    BE2019 / 5327
    In one embodiment of the present invention, the fill composition for step b) is obtained by first dry blending the mineral fill material, if any, with other dry components of the fill composition, followed by injecting the curing polymer resin, preferably as a mixture that optionally shortly before the injection was mixed with the initiator and / or with at least one and preferably all of the other liquid components of the fill composition, and then mixing the liquid and solid components of the fill composition, preferably by means of a worm gear or an Archimedes screw that brings the fill composition up to or above the coated mold while mixing. Applicants have found that this step is very easy to carry out and can be automated without problems. Applicants have found that suitable machines are available to perform this step. Applicants preferably use a mixing device derived from the Perfecta type, available from ADM Monobloc (DE).
    In one embodiment of the present invention, the mold as part of step b) is vibrated after insertion of the fill composition into the core of the coated mold, optionally in more than one cycle, each time with an interval, between which the mold can be transferred to another location, and wherein the vibration preferably takes place at a frequency of a number of cycles per minute that is in the range of 10 to 600 cycles per minute, for a total vibration time that is in the range of 15 seconds to and including 2 minutes. This additional characteristic ensures a good filling of the core volumes, through a thorough venting of the filling composition during curing. It also improves the adhesion between the two components of the product, namely the gelcoat layer and the composition that fills the core of the coated mold.
    In one embodiment of the present invention, as part of step b), after introducing the fill composition into the core of the coated mold, the amount of
    BE2019 / 5327 filled-in fill composition accurately measured and limited in such a way that, if present after shaking, it fills at least 100% of the remaining free volume of the mold, and makes up no more than 105% of that remaining free volume.
    EXAMPLE
    A stainless steel mold for a plinth is boarded with a layer of Marbocote® Spraycote FD, obtained from Marbocote Ltd (UK), which is applied with a brush. With a soft cloth, this release wax is thoroughly grounded to all unevennesses and corners of the mold, and the wax is also scrubbed until the wax layer provides a very smooth inner surface. A gelcoat layer is then applied in the molded cast, by means of a spray gun. The gelcoat layer contains 98% by weight polyester gelcoat Iso / NPG GCIG Series W-VM, obtained from Polyprocess (FR), which already contains titanium dioxide, in which also 2.0% by weight Norpol Peroxide 1, obtained from United Initiators (DE) , will be added.
    The coated mold is stored for 20 minutes in an environment with a temperature of 20 ° C to partially cure the gelcoat layer. The core of the mold is then filled with a fill composition.
    The following solids are mixed in the specified amounts by weight:
    • 56 parts quartz grains EIFEL QUARTS 1/3 from E.VICTOR-MEYER (BE), • 32 parts quartz sand M32 from SIBELCO Benelux (BE), and • 12 parts dolomite powder Madol 100 from E.VICTOR-MEYER (BE), which is a has a pH of 6.38.
    The EIFEL QUARTERS 1/3 consisted of aggregates of quartz sand size with particles in the size range of 1 to 3 mm. The SIBELCO M32 was quartz sand with a d50 of approximately 260 μm. The Madol 100 was a pure white dolomite with a d50 of approximately 10 μm.
    BE2019 / 5327
    To prepare the core fill composition, this solid mixture was mixed at a ratio of 89/11 with a polyester resin binder consisting of 96 wt% Poliplast R 96.02 obtained from Carlo Ricco & F.lli S.p.A. (IT), with 2.0 wt% Butanox M-50 added as a curing agent, obtained from Akzo Nobel Functional Chemicals (NL), which comprises MEKP as the only curing agent, and 2.0 wt% Accelerator as an accelerator NL-49P was added, obtained from Akzo Nobel Polymer Chemicals BV (NL).
    The core of the coated mold was filled with the fill composition in slight excess, and immediately vibrated to obtain a good filling and aeration, also from the core of the product. The filled mold was allowed to react further by storing it at about 18 ° C for a period of up to 40 minutes.
    The product was then removed from the mold, which was very easy thanks to the small shrinkage inherent in the use of the polyester binder. The product exhibited very smooth surfaces where the product had been in contact with a mold wall.
    The mold used was clean and still contained enough release agent, so that a new gelcoat layer could be injected into it, and from that point on, a new plinth in the same mold could be started.
    Now that this invention has been fully described, those skilled in the art will realize that the invention can be implemented with a wide range of parameters within what is claimed, without therefore departing from the spirit and scope of the invention as defined by the claims.
    权利要求:
    Claims (26)
    [1]
    CONCLUSIONS
    A method of manufacturing an article for covering floors or walls, comprising the following steps, performed in a mold:
    a) optionally applying a gelcoat layer, based on a first curing polymer resin, to the inside of the mold to obtain a coated mold,
    b) introducing into the core of the mold or into the core of the coated mold from step a) a fill composition based on a second curing polymer resin, supplemented with at least one mineral fill material, characterized in that the core of the mold article has a thickness of at least 10 mm, the core fill composition contains at least 7 weight% and at most 20 weight% curing polymer resin, relative to the dry amount of fill composition, and the fill composition contains only a single initiator in a concentration from 0.5% by weight to 5.0% by weight relative to the amount of curing polymer resin in the fill composition.
    [2]
    The method of claim 1 wherein the core of the article has a thickness of at least 15 mm, preferably at least 20 mm, more preferably at least 25 mm, even more preferably at least 30 mm.
    [3]
    The method of claim 1 or 2 wherein the core is fiber-reinforced.
    [4]
    The method according to any of the preceding claims wherein the core contains at most 19% by weight curing polymer resin.
    [5]
    The method according to any of the preceding claims wherein the second curing polymer belongs to the family of unsaturated polyester polymer resins, and wherein for the curing reaction, a vinyl monomer is preferably admixed, more preferably styrene.
    [6]
    6.
    The method according to the foregoing
    BE2019 / 5327 claim wherein the one initiator in the fill composition is an organic peroxide, more preferably methyl ethyl ketone peroxide (MEKP).
    [7]
    The method of any one of the preceding claims comprising step a) wherein the first and the second curing polymer resin belong to the same chemical family of curable polymer resins.
    [8]
    The method according to any of the preceding claims comprising step a) wherein the gelcoat layer in the coated mold of step a) is only partially cured before the coated mold of step a) is subjected to step b).
    [9]
    The method according to the preceding claim wherein the curing polymer resin of step a) is cured only until the gelcoat layer is at most dry to touch before the coated cast of step a) is subjected to step b).
    [10]
    The method according to any of the preceding claims, comprising step a) wherein the first curing polymer resin belongs to the family of unsaturated polyester polymer resins, and wherein for the curing reaction a vinyl monomer is preferably admixed, more preferably styrene.
    [11]
    The method of the preceding claim wherein the first curing polymer resin has a gel time of at least 10 minutes, preferably at least 11 minutes, and optionally at most 20 minutes, preferably at most 18 minutes, more preferably at most 16 minutes .
    [12]
    The method according to any of the preceding claims comprising step a) wherein the gel coat layer in step a) comprises at least one initiator, preferably only one initiator, preferably an organic peroxide, more preferably methyl ethyl ketone peroxide.
    [13]
    The method according to any of the preceding claims wherein the core fill composition in step b), and / or, if step a) is present the gelcoat layer in step a), further comprises an accelerator for the curing reaction, at preferred one
    BE2019 / 5327 organometallic compound, more preferably an organic cobalt salt, even more preferably cobalt octanoate.
    [14]
    The method according to any of the preceding claims wherein the mineral filler in step b) is selected from the list consisting of quartz, preferably quartz grains, more preferably quartz grains with an average particle size in the range of 1 to with 3 mm, more preferably dried quartz grains, sand, preferably sand that has been dried and sieved, dolomite powder, and mixtures or combinations thereof.
    [15]
    The method according to the preceding claim wherein the dolomite powder has a pH of at most 9.5.
    [16]
    The method according to any of the preceding claims wherein the mineral fill material in step b) comprises a mixture of a first fill material with grains having an average diameter in the range of 0.5-5 mm, with a second fill material with fine grains having an average diameter in the range of 50-500 μm.
    [17]
    The method of any one of the preceding claims wherein the mold before step b), or before step a) if the method comprises step a) is treated with a release agent.
    [18]
    The method of the preceding claim wherein the release agent comprises a polymer resin, preferably dissolved in an aliphatic hydrocarbon solvent.
    [19]
    The method according to any of the preceding claims comprising step a) wherein the gel coat layer is applied by a technique selected from the list of smears, for example with a brush and / or a roller, spraying, and combinations thereof, preferably by spraying with a spray gun under pressure.
    [20]
    The method according to any of the preceding claims, wherein at least 0.5% and at most 20% by weight are added to the polymer resin of the core and / or of the gelcoat layer, expressed on the basis of the total amount of polymer resin in the gelcoat layer or in the core, of an additional unsaturated polyester resin characterized by an elongation at break after curing of the resin, tested
    BE2019 / 5327 according to ISO 527, of at least 4.0%.
    [21]
    The method of any one of the preceding claims wherein the fill composition further comprises a substance selected from a dye, a pigment, paint flakes, metal flakes, and combinations thereof.
    [22]
    The method of any one of the preceding claims comprising step a) wherein the gel coat layer further comprises a substance selected from a dye, a pigment, a filler, paint flakes, metal flakes, and combinations thereof.
    [23]
    The method of any one of the preceding claims comprising step a) wherein the partial curing of the gelcoat layer comprises storing the coated mold in an environment with a temperature in the range of 18 ° C to 23 ° C, for a period of time in the range of 5 minutes to 6 hours, preferably at least 15 minutes, optionally at most 300 minutes.
    [24]
    The method according to any of the preceding claims wherein the fill composition for step b) is obtained by first dry blending the mineral fill material, if present with other dry components of the fill composition, followed by injecting the curing polymer resin, preferably as a mixture optionally mixed with the initiator and / or with at least one and preferably all of the other liquid components of the fill composition shortly before injection, and then mixing the liquid and solid components of the fill composition , preferably by means of a worm wheel or an Archimedes screw whereby the fill composition is brought to or above the coated mold while mixing.
    [25]
    The method according to any of the preceding claims wherein as part of step b), after inserting the fill composition into the core of the coated mold, the mold is vibrated, optionally in more than one period, each time with a interval, between which the mold can be transferred to another location, and wherein the vibration preferably takes place with a frequency of
    BE2019 / 5327 a number of cycles per minute that is in the range of 10 to 600 cycles per minute, and preferably for a total vibration time that is in the range of 15 seconds to 2 minutes.
    [26]
    26. The method of any one
    5 of the preceding claims wherein as part of step b), after introducing the fill composition into the core of the coated mold, the amount of fill composition filled is limited in such a way that, if present after shaking, they are at least 100% of the remaining free volume of the mold, and makes up no more than 105% of that remaining free volume.
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    同族专利:
    公开号 | 公开日
    BE1026291A1|2019-12-11|
    CA3100122A1|2019-11-21|
    WO2019219900A1|2019-11-21|
    EP3793810A1|2021-03-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB799613A|1955-04-01|1958-08-13|Alexander Henry Russell|Improvements in novel monolithic cast objects and method of preparing the same|
    DE2619058C3|1976-05-03|1979-05-23|Rieber Werke Heinrich Rieber Kg, 7410 Reutlingen|Wall protection device|
    US4346050A|1978-06-02|1982-08-24|Plastibeton Canada Inc.|Polymer concrete having low binder levels|
    DE3145334A1|1981-11-14|1983-05-26|Engelbrecht, Erich, 3549 Wolfhagen|Polyester resin casting|
    DE4340953C1|1993-12-01|1995-04-06|Niederberger Kg Heinrich|Ramming protection means|
    FR2756859B1|1996-12-10|1999-01-29|Aco Produits Polymeres|MODULAR PLINTH DEVICE FOR TECHNICAL PREMISES|
    NL1006957C1|1997-09-05|1999-03-08|Decocore B V|Protecting walls against damage in the food processing industry|
    BE1017613A6|2007-05-23|2009-02-03|Bumacop Nv|PROTECTION SKIRT.|
    WO2014114989A1|2013-01-28|2014-07-31|Polysto|Wall cladding or siding elements and their production|
    法律状态:
    2020-01-23| FG| Patent granted|Effective date: 20191219 |
    优先权:
    申请号 | 申请日 | 专利标题
    EP18173102|2018-05-18|
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