[go: up one dir, main page]

WO2014114989A1 - Éléments de placage ou de bardage de cloison et leur production - Google Patents

Éléments de placage ou de bardage de cloison et leur production Download PDF

Info

Publication number
WO2014114989A1
WO2014114989A1 PCT/IB2013/050726 IB2013050726W WO2014114989A1 WO 2014114989 A1 WO2014114989 A1 WO 2014114989A1 IB 2013050726 W IB2013050726 W IB 2013050726W WO 2014114989 A1 WO2014114989 A1 WO 2014114989A1
Authority
WO
WIPO (PCT)
Prior art keywords
mould
core
gel coat
curing
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2013/050726
Other languages
English (en)
Inventor
Alexandre MOREELS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
POLYSTO
Original Assignee
POLYSTO
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by POLYSTO filed Critical POLYSTO
Priority to PCT/IB2013/050726 priority Critical patent/WO2014114989A1/fr
Publication of WO2014114989A1 publication Critical patent/WO2014114989A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
    • B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
    • B29C37/0032—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied upon the mould surface before introducing the moulding compound, e.g. applying a gelcoat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/242—Moulding mineral aggregates bonded with resin, e.g. resin concrete
    • B29C67/243—Moulding mineral aggregates bonded with resin, e.g. resin concrete for making articles of definite length
    • B29C67/244—Moulding mineral aggregates bonded with resin, e.g. resin concrete for making articles of definite length by vibrating the composition before or during moulding
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F19/00—Other details of constructional parts for finishing work on buildings
    • E04F19/02—Borders; Finishing strips, e.g. beadings; Light coves
    • E04F19/026—Borders; Finishing strips, e.g. beadings; Light coves specially adapted for cushioning impacts
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F19/00—Other details of constructional parts for finishing work on buildings
    • E04F19/02—Borders; Finishing strips, e.g. beadings; Light coves
    • E04F19/04—Borders; Finishing strips, e.g. beadings; Light coves for use between floor or ceiling and wall, e.g. skirtings
    • E04F19/045—Hygienic or watertight plinths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
    • B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
    • B29C2037/0035—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied as liquid, gel, paste or the like
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F19/00—Other details of constructional parts for finishing work on buildings
    • E04F19/02—Borders; Finishing strips, e.g. beadings; Light coves
    • E04F19/04—Borders; Finishing strips, e.g. beadings; Light coves for use between floor or ceiling and wall, e.g. skirtings
    • E04F2019/0404—Borders; Finishing strips, e.g. beadings; Light coves for use between floor or ceiling and wall, e.g. skirtings characterised by the material
    • E04F2019/0422—Borders; Finishing strips, e.g. beadings; Light coves for use between floor or ceiling and wall, e.g. skirtings characterised by the material of organic plastics with or without reinforcements or filling materials

Definitions

  • the present invention relates to an improved method for the production of elements intended for the cladding of surfaces in the building industry. More particularly, the invention relates to the production of protection elements, such as plinths and bumpers/fenders which are suitable for use in hygienically sensitive areas, such as in the food industry, in the pharmaceutical industry, in hospitals, or in clean rooms, such as, for example, also in the electronics industry.
  • protection elements such as plinths and bumpers/fenders which are suitable for use in hygienically sensitive areas, such as in the food industry, in the pharmaceutical industry, in hospitals, or in clean rooms, such as, for example, also in the electronics industry.
  • the invention is also suitable for the manufacture of special cladding elements, such as decorative construction elements, more particularly special floor and wall tiles.
  • the invention also comprises certain of the possible products which may be manufactured by this method.
  • protection elements such as plinths and bumpers/fenders in the places where walls and floors merge into one another. These elements may mechanically protect the bottom part of the walls, and indirectly the walls above them, against knocks and bumps by trolleys, carts, forklifts, pallet trucks, pump trucks or pallet trucks, also known as trans pallet trucks, or also by mobile equipment or furniture, such as serving trolleys or hospital beds. Especially the corners of passages are very vulnerable, and in those locations such protection is therefore very important.
  • Firmer shock plinths may be made of concrete, but this material is relatively brittle and crumbles easily, usually has a certain porosity and is not water repellent, whereby these shock plinths are also from a hygienic point of view undesirable.
  • such concrete bumpers/fenders 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 in this context, because it confers a more hygienic and aesthetic view and also maintains this for a long time period.
  • the metal coating may for a better anchoring be shaped so that it grips around the concrete core and/or an edge thereof may be incorporated into the concrete core.
  • German Patent Specification DE 4340953 C1 describes such an embodiment, wherein a filling part consisting of polystyrene foam is used to decrease the weight of the product.
  • the metal layer may also be glued.
  • Such plinths are amongst others described in Belgian Patent Specification BE 1017613 A6. This additional metal coating is, however, cumbersome to apply.
  • DE 2619058 A1 describes a similar embodiment with a core of polyurethane (PU) foam.
  • PU polyurethane
  • This foam may be given an appropriate firmness and elasticity to support the outer metal layer, to protect it against deformation upon impact, and even to provide it with a certain cushioning and flexibility.
  • DE 29904194 U1 describes a plinth or base frame wherein a metal cover is glued to a PU rigid foam core.
  • This additional metal coating represents in all described applications a significant additional cost in terms of materials and requires additional steps in the manufacturing process.
  • the core of such plinths may use plastics as a binding agent, preferably supplemented with one or more filling materials.
  • the binding agents are preferably polymeric resins which cure by cross-linking, so that they form a solid three-dimensional molecular structure. In this way they offer a good adhesion to the filling materials, and a solid structure.
  • these resins are also water-repellent, so that the plinths may also comply with the hygienic requirements.
  • EP 848 120 A1 discloses a solid plinth formed from a composite material consisting of silicon particles coated with a polyester binder, to which a dye may 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 colouring, and/or other additional properties are to be given to the plinths by additives, then high amounts of these additives are necessary to achieve the desired result in this embodiment.
  • the properties of the core and of the surface may also not be influenced independently of each other.
  • these plinths may be further provided with an upper layer.
  • This layer may also consist of plastic, because of good chemical and water repellent properties, and which may be given a certain decorative effect by means of a pigment.
  • a very strong cross-linking polymeric resin is preferably also used for the top layer, so that ultimately a surface with high hardness is obtained.
  • NL 1006957 describes a bumper/fender which is produced by first laying a prefabricated fiber-reinforced synthetic resin profile in pre-formed mould, or by making therein a top layer of a fibre reinforced coating.
  • This top layer is made of a food-safe coating consisting of polyester resin mixed and filled up with fibres and/or glass fleece, produced to meet a particular impact strength.
  • the mould is filled with a composition consisting of very fine gravel parts, or other filling materials, and a polyester resin or other synthetic resin. Also accessories such as inside and outside corners and end pieces are described.
  • NL 1006957 is not concerned with the compatibility between the binders of the top layer and of the core, nor with the adhesion between the core and the top layer of the bumper/fender.
  • DE 3145334 A1 describes a stairs step which is produced by applying on a glass plate a thin layer of a mixture on the basis of a resin "Fein harshharz Nr. 325 ", which at 20°C ambient temperature has a gelation time of eight to twelve minutes, within which time the layer must have been applied. About 20 minutes, at the latest two hours, after the application of the thin layer on the glass, into the mould is poured the material for the filling layer, which is based on a polyester resin, and which is subsequently allowed to polymerize. The inventors have found that the adhesion between the core and the top layer of DE 3145334 may be further improved.
  • the present invention has as the object to avoid or at least alleviate the problems described above, and/or provide improvements in general.
  • the invention provides more particularly a method for the production of an article for the cladding of floors or walls, comprising the steps of:
  • step b) introducing into the core of the' coated mould of step a) a filling composition which is based on a curing polymer resin supplemented with at least one mineral filler,
  • step a) and step b) are of the same chemical family of curable polymeric resins
  • step b) wherein the gel coat layer in the coated mould of step a) is only cured partially before the coated mould of step a) is subjected to step b),
  • step b) characterized in that the curing polymer resin of step a) is cured only until the gel coat layer is at most touch dry, before the coated mould of step a) is subjected to step b).
  • the method according to the present invention is extremely simple, and moreover, provides without any layer of glue an exceptionally good adhesion between the gel coat upper layer and the core of the produced product.
  • step a) and step b) may be set independently from each other, so that they optimally meet the stated requirements and, at the same time may be adjusted to each other to be able to produce a product with the desired properties in a simple and fast way, and this with relatively little human intervention.
  • the present invention provides an element for the cladding of floors or walls which may be produced by the method according to the present invention, and which consists of a core of a composition which is based on unsaturated polyester resin, supplemented with at least one mineral filler material, at least partially surrounded by an outer layer based on a gel coat, which is also based on unsaturated polyester resin, and which element is selected from a decorative wall tile or floor tile and a plinth or bumper/fender, wherein in the case of the decorative floor tile or wall tile at least one dye or pigment has been added to the gel coat, and/or whereby to at least one surface of the mould at least partly a varying relief shape is given, and wherein in the case of the plinth or bumper/fender, and optionally also to the decorative wall or floor tile, to the polymer resin of the core and/or of the top layer at least 0.5% and at most 20% by weight is added, expressed on the basis of the total amount of polymer resin in the top layer or in the core, of an unsaturated
  • these components are not subject to rotting and/or corrosion, ensuring their longer life time.
  • decorative wall tiles and floor tiles may be produced, which are highly resistant to the influence of weather conditions, especially to acid rain, but also to UV radiation, biological wear, and other chemical influences.
  • Such floor tiles and wall tiles are also very easy to maintain and to clean because they are highly resistant to a wide range of detergents and surfactants, and to the other additives which are used in cleaning products.
  • the water-repellent characteristics of the gel coat upper layer play an important role. Because of their high hardness, they may also easily be cleaned with a high-pressure water lance, without this leading to scratching and/or loss of gloss:
  • the decorative possibilities are very broad, because the choice of pigments which may be added to the gel coat layer is virtually unlimited.
  • floor tiles and wall tiles thus offer an important alternative for the cladding of floors or walls, especially exterior floors and exterior walls, and by their extraordinary mechanical properties, especially impact strength and chemical resistance, they are in many aspects better than many of the other alternatives that are offered for floor or wall cladding.
  • construction elements are therefore particularly suitable for cladding large outdoor floors around, or the exterior walls of buildings which are larger than typical in a residential context, such as public service and/or industrial buildings, and wherein said decorative elements by their appearance, luster, and persistence may significantly increase the appearance or the prestige of the clad building and/or its environment, and may guarantee this effect for a long time.
  • the plinths or bumpers/fenders according to the present invention have the advantage that they run less risk of damage during assembly, because the gel coat upper layer has some flexibility, is less brittle, and contains less residual stress. When mounting with a tool, flakes will therefore less easily desquamate, making sure the aesthetic and hygienic effect is better preserved.
  • the products produced according to this method are also easy to repair, with a simple polyester kit having the appropriate colour.
  • poly- a quantity greater than 1 is meant. If only integers are applicable, "poly” means the same as “two or more” or “at least two (2)”.
  • thermosets or thermosetting polymers or polymer resins may be used within the framework of the present invention.
  • Alkyd resins, phenol formaldehyde (PF) resins, diallyl phthalate (DAP) resins, melamine-formaldehyde (MF) resins, polyester resins, and urea-formaldehyde (UF) resins are possible.
  • the curing polymer resin of step a) and step b) belong to the family of unsaturated polyester polymer resins, and wherein preferably for the curing reaction a vinyl monomer has been incorporated, more preferably styrene.
  • Unsaturated polyesters are curing polymer resins. Generally, they are copolymers obtained by the polymerisation of one or more polyols, usually diols, such as monoethylene glycol (MEG), with unsaturated dicarboxylic acids such as maleic acid or fumaric acid, and/or the anhydrides thereof.
  • partially saturated and/or aromatic acids and/or their anhydrides may be used, such as the various forms of phthalic acid or phthalic acid anhydride.
  • the double bond of the unsaturated polyesters reacts during curing with a vinyl monomer, usually styrene, so that a three-dimensional cross-linked structure is formed.
  • the cross-linking is usually set in motion by an exothermic reaction in which an organic peroxide may be used as an initiator, often also called less accurately the catalyst, such as methyl ethyl ketone peroxide, benzoyl peroxide or dibenzoyi peroxide.
  • the initiator usually acts by releasing a free radical which initiates the polymerization or chain reaction.
  • vinyl monomer usually styrene, a-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, alone or in mixtures with each other are being used.
  • Other vinyl monomers which may be used are the alkyl-styrenes, and other allyl, acrylate or methacrylate esters.
  • Suitable unsaturated polyesters are commercially offered by many companies, and are available in a wide range of properties. Such polyesters are also commercially available in mixtures with styrene so that they may immediately be used as a binder in the step b) of the method according to the present invention.
  • a gel coat layer within the context of the present invention is preferably a gel coat layer based on a polyester, such as obtained by the esterification of a polyvalent carboxylic acid with a polyol, which means a chemical substance having at least two hydroxyl (OH) groups.
  • the polyvalent carboxylic acid of the polyester resin of the gel coat layer or of the core of the article may be aliphatic or aromatic.
  • the applicants prefer to use a polyester formed from an aromatic polyvalent carboxylic acid. Suitable candidates are, for example, phthalic acid, also called orthophthalic acid, isophthalic acid and/or terephthalic acid, but also acids with several benzene nuclei are possible.
  • the applicants prefer a gel coat which is based on orthophthalic acid, most preferably based primarily on orthophthalic acid.
  • polyols which may be used in the polyester according to the present invention. Suitable are, for example, ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,3-butanediol, ,4-butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, and bis- ⁇ -hydroxypropyl)ether of bisphenol A.
  • the applicants prefer a polyol which has only two hydroxyl functions per molecule.
  • Suitable candidates are available in large numbers, such as ethylene glycol, mono-ethylene glycol, ethylene glycol oligomers such as diethylene glycol, triethylene glycol, and tetraethylene glycol, ,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, ,2-pentanediol, 2-methyl-2,4-pentanediol, neopentyl glycol, bisphenol A, the bis-( -hydroxypropyl)ether of bisphenol A, and others.
  • a divalent polyol together with a divalent carboxylic acid, gives a so-called "linear" polyester. This avoids excessive cross-linking, such that the viscosity of the polyester is kept quite low, so that the substance which contains the polyester is sufficiently well spreadable or sprayable, or that it flows sufficiently easily enough before the curing step, so that a good adaptation to the mould, or a good filling of the given space, may readily be achieved, with a minimum of effort.
  • the applicants prefer a gel coat which is primarily based on a resin made from virtually pure isophthalic acid together with neopentyl glycol.
  • unsaturated carboxylic acids In the manufacture of the unsaturated polyester, often unsaturated carboxylic acids are used. Suitable are ethylene-like ⁇ , ⁇ - unsaturated dicarboxylic acids, for example maleic acid, fumaric acid, citraconic acid, itaconic acid, mesaconic acid and the like, or the anhydrides thereof. In the production of the unsaturated polyester, often also saturated carboxylic acids are 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 butanoic divalent acid.
  • monohydric alcohols or acids may be used in the production of the polyester monomers which may be used as raw materials in the present invention.
  • these components may be used either straight chained or branched.
  • polyhydric alcohols such as glycerine, trimethylolpropane, pentaerythritol or the like, for obtaining, where possible, already some cross-linking in the monomer.
  • the polyesters are often offered as a solution in a liquid vinyl monomer, preferably styrene.
  • the formulation is subsequently diluted, also called “modified” by the addition of dicyclopentadiene (DCPD).
  • DCPD dicyclopentadiene
  • This DCPD provides additional cross-linking of the finally cured polymer, and because the reagent is a liquid, it allows to use less styrene for reaching the same low viscosity for the gel coat, in order to allow proper processing.
  • the applicants thereby prefer sometimes a "preaccelerated” version of this gel coat, wherein an amount of catalyst is added to obtain a faster curing reaction.
  • this gel coat preferably has a viscosity of 2000 to 30000, preferably from 5000 to 25000, more preferably of from 8000 to 20000, and most preferably from 10000 to 18000 centipoise (cPs) at 20°C, measured according to NFT 51 210, with a Brookfield RVF 100 meter, using a No. 5 spindle at 20 revolutions per minute.
  • cPs centipoise
  • the applicants prefer that these belong to the same chemical family as the resin which acts as the binder in the gel coat.
  • the applicants thereby thus prefer to also use a polyester, preferably an unsaturated polyester.
  • These products are typically offered as a solution in styrene monomer, which is liquid and may easily be pumped. Suitable products are for example VIAPAL VUP 4778/55 available from Cytec Surface Specialties GmbH, with approximately 44 wt% styrene, Distriton 110 mod available from Lonza SpA, and ENYDYNE ® D 20-321 from Cray Valley.
  • the applicants prefer to use resins from the family Resin Poliplast R 96 Carlo Ricco' & F.lli S.p.A.
  • the applicants preferably use as the principal resin a polyester resin having, prior to the curing reaction, a viscosity at 25°C of 100-600 mPa.s, more preferably of 200-500 mPa.s, more preferably of 250-460 mPa.s, yet more preferably of about 300-400 mPa.s, and most preferably of about 320-360 mPa.s.
  • the polyester resin composition contains preferably 25-50% by weight of styrene, more preferably 30-40 wt%, and yet more preferably 31-33 wt% styrene.
  • an accelerator for accelerating the curing reaction frequently is used.
  • Suitable are, for example, the salts of cobalt, manganese, vanadium and iron, ⁇ -diketones selected from derivatives of acetyl acetone, derivatives of aceto acetamide, and esters of aceto acetic acid, but also tertiary aromatic amines such as, for example, dimethyl aniline, dimethyl-p-toluene, diethyl aniline, phenyl diethyl aniline, phenyl-diethanol amine, and the like. These are typically used in concentrations of 0.05-1.0 parts by weight per hundred parts of resin. With metal components thus usually only the concentration of the metal is intended.
  • cobalt more preferably a cobalt compound, more preferably an organometallic cobalt compound.
  • cobalt octanoate containing cobalt at 6% by weight, which is effective in small amounts, such as from 0.10-0.30 wt%, preferably 0.15-0.20% by weight, based on the resin.
  • this accelerator is very suitable in these concentrations, together with 1.0-3.0 wt% MEKP initiator, preferably 1.5-2.5% by weight of MEKP.
  • the cross-linking or curing reaction with unsaturated polyester resins is preferably a free radical polymerization reaction.
  • This reaction is preferably initiated by an initiator, also called curing agent, a.k.a. hardener or catalyst.
  • initiator for the curing reaction preferably peroxides are used, often a combination of several peroxides, more preferably organic peroxides because they are less volatile, and because they may often be supplied as a liquid.
  • Suitable are, for example, hydrogen peroxide, benzoyl peroxide, lauryl peroxide, dicumyl peroxide, p-tertiary butyl perbenzoate, acetyl acetone peroxide (AAP), methyl isobutyl ketone peroxide, and the like.
  • AAP acetyl acetone peroxide
  • MEKP methyl ethyl ketone peroxide
  • MEKP gives a reliable performance at ambient temperature and at room temperature.
  • the MEKP is normally supplied as a 30-40 wt% solution in a suitable solvent such as, for example, dimethyl phthalate ester.
  • a phlegmatiser is added, which is a substance which stabilizes the relatively unstable peroxide during storage and for transport and handling, until it is expected to carry out its action.
  • a phlegmatiser for example, 2,2,4-trimethyl-1 ,3-pentanediol diisobutyrate, also known as TXIB, may be used.
  • TXIB 2,2,4-trimethyl-1 ,3-pentanediol diisobutyrate
  • other organic compounds having little to no of the relatively less stable -CH 2 - groups may be used.
  • the initiator brings the advantage that the cross-linking or curing reaction may be initiated at ambient and/or room temperature. As a result, extremely high temperatures are avoided, which could otherwise lead to discolouration, and even to a loss of the chemical and mechanical properties of the product.
  • This curing agent is preferably used as a 30-40 wt% solution in 40-50 wt% dimethyl phthalate, along with a 10-20% TXIB as phlegmatiser or stabilizer.
  • a suitable curing agent solution is, for example, available as Andonox KP-100 of the company Norac ANDOS AB. Curing agent concentrations referred to in this document are intended to be the concentrations of the curing agent solution, including the solvent and stabilizer, and any other ingredients of the solution.
  • the applicants prefer to use a composition which is also based on unsaturated polyester resin as a binder, together with at least one mineral filler.
  • the binding material belongs to the same chemical family of curing polymer resins as the polymer resin chosen for the gel coat, it is preferably also an unsaturated polyester polymer resin.
  • a vinyl monomer is also mixed in, more preferably also styrene.
  • step b) a composition comprising as binder 10-30 wt% polyester resin, more preferably 12-25 wt%, still more preferably 15-20 wt%, and most preferably from about 17 wt% polyester resin.
  • step b) also preferably at least one initiator or curing agent.
  • a peroxide is used, more preferably an organic peroxide, such as those already mentioned above.
  • the applicants use methyl ethyl ketone peroxide, preferably in solution, together with a stabilizer.
  • concentrations of curing agent referred to in this document are meant to be the concentrations of the curing solution, including the solvent and stabilizer, and any other eventual ingredients of the solution.
  • the applicants prefer as the curing agents methyl ethyl ketone peroxide (MEKP) together with yet another peroxide.
  • MEKP methyl ethyl ketone peroxide
  • cumyl hydroperoxide as a second curing agent.
  • These curing agents are preferably used as a 25-40% solution in dimethyl phthalate, wherein the MEKP preferably constitutes 27-37 wt%, and cumyl hydroperoxide possibly constitutes 6-7 wt% of the solution, together with a 10- 20% phlegmatiser or stabilizer, which could be, for example, methyl benzoate.
  • a suitable curing solution is for example available as Andonox KP-LE of the company Syrgis Performance Initiators AB.
  • an initiator having a somewhat lower activity which gives rise to a lower exotherm upon curing, such that the risk of stress, shrinkage and cracking decreases, which is especially important for thicker objects, such as the core of the elements which may be produced by the method according to the present invention.
  • These initiators are preferably used in conjunction with cobalt-based accelerators, such as those which have already been discussed above.
  • the gel coat layer in step a) and/or the filling composition for the core in step b) further comprises at least one initiator, preferably an organic peroxide, more preferably methyl ethyl ketone peroxide (MEKP).
  • initiator preferably an organic peroxide, more preferably methyl ethyl ketone peroxide (MEKP).
  • the curing agent in a concentration of 1.0-5.0 wt% of the composition of step b), preferably 1.2- 4.0 wt%, more preferably 1.4-3.0 wt%, even more preferably 1.5-2.5 wt% , and even more preferably 1.8-2.2 wt%, typically about 2.0 wt%, and this on the basis of the weight of the total amount of resin, including the other monomers such as the vinyl monomer and/or DCPD, which is introduced into the composition.
  • an accelerator preferably a cobalt accelerator, preferably an organic salt of cobalt, more preferably cobalt octanoate.
  • a suitable accelerator is for example Accelerator NL-49P available from Akzo Nobel Polymer Chemicals BV. This is a solution of cobalt(ll)-2-ethyl- hexanoate into an aliphatic ester, which contains about 1 wt% cobalt, or 5- 10 wt% cobalt(ll)-2-ethyl-hexanoate, which may also be called cobalt octanoate.
  • TXIB aliphatic ester
  • EGECat Cobalt 1% available from EGE KIMYA AS in Turkey. This comprises 0.9-1.1% by weight of cobalt metal dissolved in a hydrocarbon solvent.
  • the gel coat layer in step a) and/or the filling composition for the core in step b) further comprises an accelerator for the curing reaction, preferably an organometallic compound, more preferably an organic cobalt salt, still more preferably cobalt octanoate.
  • an accelerator for the curing reaction preferably an organometallic compound, more preferably an organic cobalt salt, still more preferably cobalt octanoate.
  • mineral filler material most preferably only mineral filling material, mainly because this is chemically less active, usually even inert, and hence there is no influence on the cross-linking of the filler material and/or curing reaction.
  • mineral fillers usually have a lower porosity than for example plastics, whereby they take up less of the binding agent and the amount of resin does not have to be increased to compensate for such absorption.
  • An additional advantage is the generally common availability of suitable mineral fillers.
  • the mineral filler in step b) is selected from the list consisting of quartz, preferably quartz grains, more preferably quartz grains having an average particle size in the range of 1 to 3 mm, more preferably dried grains of quartz, sand, preferably sand which was sieved, washed and dried, and mixtures or combinations thereof:
  • a combination of a first filler, which comprises larger grains, with a second filler having a finer grain size gives a very good degree of filling, and yet allows to limit the amount of polymer resin which is required as the binder.
  • the applicants prefer to use a mixture of a first filler with grains which have 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, more preferably not more than 3 mm, with a second filler with fine grains having an average diameter in the range of 50-500 pm, preferably 100- 400 ⁇ , more preferably 150-350 pm, more preferably 200-300 pm and at still more preferably 235-280 pm.
  • the filling properties of the filler material may be further improved by the addition of a third filler with an even smaller grain size, which is suitable for also filling the smaller spaces between the grains of the second filler.
  • the inventors prefer the third filler having an average grain diameter (D50) in the range of 5-200 pm, preferably 10-100 pm, more preferably 20-70 pm and even more preferably 30-50 pm.
  • D50 average grain diameter
  • Many suitable filler powders are available.
  • dolomite which consists for about 99 wt% of calcium magnesium carbonate CaMg(C0 3 ) 2 , such as dolomite powder Microdol A 70 available from OMYA Benelux.
  • This powder also has the advantage that it also serves as a pigment, and makes the colour of the composition lighter, which is favourable in order to have no effect on the colour which the gel coat layer brings.
  • the dried silica 1-3 for example 1-3 EIFEL quartz
  • treated sand for example, M32 SIBELCO quartz sand
  • dolomite powder at example OMYA Microdol A70
  • the inventors prefer that the mould be rubbed in with an external release agent or a release wax (also called “mould release agent” or “mould release wax”).
  • the mould is, before the application of the gel coat layer in step a), rubbed in with a release agent (mould release agent, release wax).
  • This release wax is preferably polished into the mould, as this gives a smoother outer surface of the produced article, which increases the aesthetic appearance, but also the hygienic aspect of the object.
  • silicone-free formulations to avoid unwanted colour effects on the cured gel coat layer.
  • fractions which are not too heavy preferably the "middle distillate" fractions, also known as kerosene or diesel oil types. Heavier fractions, such as waxes, may then be dissolved therein. Even more suitable are those fractions which are also desulphurized down to a low content of sulphur, 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.
  • Ce-Sense Slip-X10 available from Brands Structural Products (NL).
  • the release agent may be applied by hand or by spraying.
  • the release agent is first left to dry before it is polished to a high gloss.
  • the material is preferably thinly applied 2-3 times to obtain a good coverage and a uniform thickness.
  • this external release agent is applied in a very homogeneous thin layer with a very smooth top surface. This ensures that the top surfaces of the product of the method which were in contact with a wall of, the mould, obtain a very smooth aspect, and even become glossy.
  • the gel coat layer in step a) is applied by means of a technique selected from the list of spreading, for example, with a brush and/or roller and/or a soft cloth, spraying, and combinations thereof.
  • the resins which are used in the context of the present invention may also be mixtures of two or more resins having different properties. In this case, the above description of the resins holds for the principal resin in such a mixture.
  • the gel coat layer in step a) and/or the filling composition for the core in step b) further comprises 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 unsaturated polyester resin which is characterized by an elongation at break after curing of the resin and tested according to ISO 527 of at least 4.0%.
  • the elongation at break of this additional unsaturated polyester resin is at least 5.0%, more preferably at least 10%, even more preferably at least 20%, preferably at least 30%, more preferably at least 40%, and still more preferably at least 45%.
  • this resin may be chosen so that the elongation at break is not more than 100%, preferably not higher than 75%, and more preferably not higher than 60%. In this way, the risk is reduced that the hardness would be reduced.
  • the resin is usually obtained by making the polyester chain somewhat longer, preferably by incorporation of longer polyol monomers, preferably polyol monomers of which the chains are not strictly linear, but exhibit angles.
  • oligomers thereof preferably those which contain one or more ether functions as part of the chain.
  • the inventors preferably use for the core not more than 15% by weight of this additional polyester resin, and this primarily because the hardness of the final product should not decrease too much. More preferably, the inventors use a maximum of 10% by weight, even more preferably at most 5% by weight, and even more preferably at most 3% by weight of this additional resin, and this relative to the total amount of resin which is used in the filling composition of the core.
  • the inventors preferably use not more than 16% by weight of this additional polyester resin. More preferably, the inventors use a maximum of 12% by weight, even more preferably at most 9% by weight, and yet more preferably at most 7% by weight of this additional resin, and this relative to the total amount of resin which is used in the filling composition of the gel coat layer.
  • the inventors preferably use in the gel coat layer at least 2% by weight, more preferably at least 3% by weight and even more preferably at least 4% by weight, expressed on the same basis. This quantity has been found to be sufficient for giving the desired properties to the gel coat top layer.
  • this additional resin may also be used as pre-mixed.
  • This additive gives a higher elasticity to the cured gel coat layer and/or to the cured core.
  • This offers several advantages.
  • the addition to the core offers the advantage that residual stresses are reduced 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 gel coat layer. The stresses may be reduced, and less likely lead to cracks, so that there are much less end-products which have to be rejected or further treated to remain useful.
  • This addition of the additional polyester resin also has the advantage that, when installing the cladding element, which, depending on its size, may have a considerable weight, and, therefore, often has to be placed with the help of mechanical tools such as a crowbar, there is less risk for desquamation of the gel coat layer, so that the aesthetic effect is better preserved, and fewer elements turn useless during the installation and must be replaced and/or discarded.
  • the gel coat layer further contains a substance which is selected from a dye, a pigment, a filler, paint chips, metal flakes, and combinations thereof.
  • the gel coat layer may be pigmented with a wide choice of pigments, in every available colour, for example, with each of the available RAL colours.
  • a dye optionally also a transparent version is possible.
  • the partial curing of the gel coat layer comprises the retention of the coated mould in an environment with a temperature in the range of from 10°C to 50°C, preferably at least 15°C and more preferably at least 18°C, and optionally not more than 35°C, preferably at most 30°C, even more preferably at most 25°C, and still more preferably at most 23°C.
  • the storage preferably occurs for a period of time of at least 2 minutes, preferably at least 5 minutes, even more preferably at least 10 minutes, and yet more preferably at least 15 minutes.
  • the retention takes no longer than 24 hours, preferably no longer than 18 hours, more preferably no longer than 12 hours, and even more preferably at most 6 hours.
  • the filling composition for step b) is obtained by first dry blending the mineral filler material, if present with other dry ingredients of the filling composition, followed by the injection of the curable polymer resin, preferably as a mixture which possibly shortly before the injection was mixed with the initiator and/or with at least one and preferably all of the other liquid ingredients of the filling composition, and subsequently mixing the liquid and the solid ingredients of the filling composition, preferably by means of a worm wheel or an Archimedes screw which brings the filling composition during the mixing at or above the coated mould.
  • This step is very easy to carry out and may readily be automated.
  • suitable machines are offered to execute this step.
  • the applicants prefer to use a mixing machine which is derived from the type Perfecta, available from the company ADM Monobloc (DE).
  • step b) after the insertion of the filling composition in the core of the coated mould, the mould is being vibrated, possibly in more than one cycle, each time with an interval, between which the mould may be transferred to a different location, and wherein preferably the vibration occurs at a frequency of a number of cycles per minute which is in the range of 10 to 600 cycles per minute, and this for a total vibration time which is in the range of 15 seconds to 2 minutes.
  • This additional feature provides for a good filling of the core volumes, by a thorough deaeration of the filling composition under curing. It also improves the adhesion between the two components of the product, namely the gel coat layer and the composition which fills the core of the coated mould.
  • step b) upon introduction of the filling composition into the core of the coated mould, the amount of introduced filling composition is accurately proportioned and limited in such a way that it fills, if present after shaking, at least 100 % of the remaining free volume of the mould and up a maximum of 105% of that remaining free volume.
  • the present invention provides a product which may be produced according to the method which constitutes an embodiment of the present invention.
  • the present invention provides an element for the cladding of floors or walls which may be produced by the method according to any one of the preceding claims, and which consists of a core of a composition which is based on unsaturated polyester resin, supplemented with at least one mineral filler material, at least partially surrounded by an outer layer based on a gel coat, which is also based on unsaturated polyester resin, and which element is selected from a decorative floor tile or wall tile, and a plinth or bumper/fender, wherein in the case of the decorative floor- or wall tile, to the gel coat at least one dye or pigment has been added, and/or to at least one surface of the mould at least partly a varying relief shape is given, and wherein in the case of the plinth or bumper/fender, but optionally also to the decorative floor tile or wall tile, at least 1.0% and at most 18% by weight is added to the polymer resin of the core and/or of the top layer, expressed on the basis of the total amount of polymer resin in the top layer or in the core, of
  • the element according to the present invention with this additional resin brings the advantage that less residual stresses remain after curing and the consequent shrinkage. That way there is less risk of cracking, and thus indirectly of inferior and even potentially useless end products.
  • the inventors find t possible to use this additional resin only in the core or only in the gel coat layer. Yet, they prefer to use this additional resin in both, i.e. in both the core as well as in the gel coat top layer. In this way, all the advantages afforded by this additional resin may be achieved together.
  • the present invention provides a plinth or bumper wherein the gel coat layer also comprises 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 unsaturated polyester resin which is characterized by an elongation at break after curing of the resin and tested according to ISO 527 of at least 4.0%. Preferred embodiments of this additional resin have already been explained earlier in this document.
  • This plinth or bumper/fender brings the advantage that it gives less risk for desquamation of the gel coat layer when installing it by means of mechanical devices. It leads to less damage, better preservation of the aesthetic characteristics of the product after installation, and a lower risk of rejected elements which need to be replaced and/or discarded.
  • This additional resin may be blended into the ordinary resin.
  • the inventors use for the gel coat layer a pre-mixed blend with 5% weight of the additional resin.
  • a polyester resin is, for example, based on isophthalic acid and neopentyl glycol and a flexible isophthalic resin.
  • a suitable mixture is for example available as GC 875, Gel Coat ISO-NPG, NTG 193A from the company Nord Composites.
  • the inventors prefer to use a pre-blended resin with 10-20% weight of the additional resin, and they themselves prefer to mix this mixture in a ratio of 20 parts by weight of the mixture with 80 parts by weight of the main resin for the filling composition of the core.
  • Another suitable resin is available as VIAPAL UP 179 MT/57 from the company Cytec Surface Specialties.
  • the element according to the present invention may also be clad with a metal cladding, preferably a stainless steel cladding.
  • This cladding may be mechanically anchored to the element by, for example, providing edges which grip around the element.
  • the cladding may also be chemically anchored to the element, such as by gluing.
  • a glue the applicants prefer to use a glue based on modified silane (SiH4) compounds.
  • SiH4 modified silane
  • the glue adhesion is subsequently achieved because water, for example originating from air humidity, reacts with the silane compounds and thereby achieves polymerization, and preferably also cross-linking.
  • Such adhesives are also called SMP (Silyl Modified Polymer), also known as MS-polymer (Modified Silane Polyether).
  • a stainless steel mould for a plinth is polished with a layer of Ce-Sense Slip-X10 obtained from Brands Structural Products. With a soft cloth, this release is wax very thoroughly spread into all irregularities and corners of the mould, and the wax is additionally polished until the wax layer provides a very smooth inner surface.
  • a gel coat layer Into the polished mould is subsequently applied a gel coat layer, by means of a spray gun.
  • the gel coat layer contains 98 wt% polyester gel coat GC 875 9270 obtained from Nord Composites (FR), in which was added 2.0 wt% Andonox KP-100 obtained from Norac ANDOS AG.
  • the coated mould is stored during 20 minutes in an environment with a temperature of 20°C to partially cure the gel coat layer. Subsequently, the core of the mould is filled with a filling composition.
  • this solid mixture was blended in a ratio of 79/21 with a polyester resin binder, consisting of 96 wt% Poliplast R 96.02 obtained from Carlo Ricco' & F.lli S.p.A. (IT), wherein as hardener 2.0 wt% Andonox KP-LE obtained from Syrgis Performance Initiators AB (SE) and as accelerator 2.0 wt% Accelerator NL-49P obtained from Akzo Nobel Polymer Chemicals BV (NL) were added.
  • a polyester resin binder consisting of 96 wt% Poliplast R 96.02 obtained from Carlo Ricco' & F.lli S.p.A. (IT), wherein as hardener 2.0 wt% Andonox KP-LE obtained from Syrgis Performance Initiators AB (SE) and as accelerator 2.0 wt% Accelerator NL-49P obtained from Akzo Nobel Polymer Chemicals BV (NL) were added.
  • the core of the coated mould was filled with a slight excess of the filling composition, and immediately vibrated to promote a good filling and to obtain a good deaeration of also the core of the product.
  • the filled mould was allowed to further react by storage at about 18°C during a period of about 2 hours.
  • the product was subsequently removed from the mould, which was easily possible thanks to the small shrinkage inherent with the use of the polyester binder.
  • the product exhibited very smooth surfaces where the product had been in contact with a wall of the mould.

Landscapes

  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Public Health (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un procédé de production d'un article destiné au placage de planchers ou de cloisons, comprenant les étapes consistant à : a) appliquer une couche de revêtement sous forme de gel, à base d'une résine polymère durcissable, sur l'intérieur d'un moule afin d'obtenir un moule revêtu, b) introduire au cœur du moule revêtu selon l'étape a) une composition de remplissage à base de résine polymère durcissable complémentée d'au moins une charge minérale, les résines polymère durcissables selon l'étape a) et l'étape b) appartenant à la même famille chimique de résines polymères durcissables, et la couche de revêtement sous forme de gel dans le moule revêtu selon l'étape a) n'étant que partiellement durcie jusqu'à ce que la couche de revêtement sous forme de gel soit au plus sèche au toucher avant que le moule revêtu selon l'étape a) ne soit soumis à l'étape b). L'invention concerne également un élément destiné au placage d'un plancher et de cloisons.
PCT/IB2013/050726 2013-01-28 2013-01-28 Éléments de placage ou de bardage de cloison et leur production Ceased WO2014114989A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/IB2013/050726 WO2014114989A1 (fr) 2013-01-28 2013-01-28 Éléments de placage ou de bardage de cloison et leur production

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2013/050726 WO2014114989A1 (fr) 2013-01-28 2013-01-28 Éléments de placage ou de bardage de cloison et leur production

Publications (1)

Publication Number Publication Date
WO2014114989A1 true WO2014114989A1 (fr) 2014-07-31

Family

ID=47997601

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2013/050726 Ceased WO2014114989A1 (fr) 2013-01-28 2013-01-28 Éléments de placage ou de bardage de cloison et leur production

Country Status (1)

Country Link
WO (1) WO2014114989A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019219900A1 (fr) 2018-05-18 2019-11-21 Polysto Perfectionnement apporté à des éléments de revêtement mural et de bardage
US11485094B2 (en) 2018-05-18 2022-11-01 Polysto Process for the production of an article for the cladding of floors or walls
CN115335580A (zh) * 2020-03-26 2022-11-11 达陶公司 用于制造外圆角瓷砖的方法和外圆角瓷砖

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3145334A1 (de) * 1981-11-14 1983-05-26 Engelbrecht, Erich, 3549 Wolfhagen Polyesterharz-giesskoerper
EP0727304A2 (fr) * 1995-02-17 1996-08-21 Muovilami Oy Procédé de fabrication d'un élément de structure et élément ainsi obtenu
US7431789B2 (en) * 2003-07-15 2008-10-07 Vrac, Llc Covalently compatible in-mold coating compositions for use with epoxy

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3145334A1 (de) * 1981-11-14 1983-05-26 Engelbrecht, Erich, 3549 Wolfhagen Polyesterharz-giesskoerper
EP0727304A2 (fr) * 1995-02-17 1996-08-21 Muovilami Oy Procédé de fabrication d'un élément de structure et élément ainsi obtenu
US7431789B2 (en) * 2003-07-15 2008-10-07 Vrac, Llc Covalently compatible in-mold coating compositions for use with epoxy

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019219900A1 (fr) 2018-05-18 2019-11-21 Polysto Perfectionnement apporté à des éléments de revêtement mural et de bardage
US11485094B2 (en) 2018-05-18 2022-11-01 Polysto Process for the production of an article for the cladding of floors or walls
CN115335580A (zh) * 2020-03-26 2022-11-11 达陶公司 用于制造外圆角瓷砖的方法和外圆角瓷砖

Similar Documents

Publication Publication Date Title
US11485094B2 (en) Process for the production of an article for the cladding of floors or walls
EP2097479B1 (fr) Charge pulvérulente organique utile comme remplacement d'une charge minérale dans des composites
US6548157B2 (en) Stone-like laminates
WO2014114989A1 (fr) Éléments de placage ou de bardage de cloison et leur production
AU2010214758A1 (en) Colored Material Coated Transparent Chip for Artificial Stone, Method of Preparing Same, and Artificial Stone including Same
US5504126A (en) Mineral-like coating and methods of using same
EP3147303A1 (fr) Produit de surface solide comprenant un isocyanate aliphatique et procédé de fabrication de celui-ci
EP3793810B1 (fr) Procédé de production de revêtements muraux et d'éléments de parement
US8679623B2 (en) Cast polymer and recycled glass composite article
Yalcin Hollow glass microspheres in sheet molding compounds
KR20190050275A (ko) 내광성이 개선된 인조대리석
BE1019929A5 (nl) Muur-of wandbekledingelementen en hun productie.
JP2011202123A (ja) 不飽和ポリエステル樹脂組成物及び成形品
KR101542577B1 (ko) 친환경 미끄럼방지 포장재
KR102447482B1 (ko) 고분자 합성반응에 식물성 천연재료를 사용한 결합제로 구성된 친환경 크리트 바닥마감재 및 그 시공방법
AU2024100012A4 (en) Composite slab comprising recycled glass
KR20100029503A (ko) 시멘트를 포함하는 인조 대리석 및 그 제조방법
KR20000036095A (ko) 사물 형성을 위한 신규한 중합체 첨가제
US7498374B2 (en) Cast polymer and method of making the same
JP2006117884A (ja) 不飽和ポリエステル樹脂組成物及び複合被覆体
JP2006342266A (ja) ラジカル硬化性樹脂組成物及びその硬化方法
IT202000015994A1 (it) Materiale composito comprendente un materiale a base di sughero e un materiale polimerico
WO1995009875A1 (fr) Composition polymere complexe thermodurcie
JPH031943A (ja) 耐熱水性に優れた御影調成形体
JPS5986668A (ja) 被覆用硬化型樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13711955

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13711955

Country of ref document: EP

Kind code of ref document: A1