WO2002042373A1 - Produit laminaire renforce d'aspect granite a base d'aminoplaste thermodurcissable - Google Patents

Produit laminaire renforce d'aspect granite a base d'aminoplaste thermodurcissable Download PDF

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Publication number
WO2002042373A1
WO2002042373A1 PCT/NL2001/000807 NL0100807W WO0242373A1 WO 2002042373 A1 WO2002042373 A1 WO 2002042373A1 NL 0100807 W NL0100807 W NL 0100807W WO 0242373 A1 WO0242373 A1 WO 0242373A1
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WO
WIPO (PCT)
Prior art keywords
granite
look
granules
laminar product
mixture
Prior art date
Application number
PCT/NL2001/000807
Other languages
English (en)
Inventor
Jacobus Baetsen
Hermanus Peter Snuverink Ook Lansink
Renatus Petrus Maria Donkers
Ronnie Mathias Gerardus Riedel
Cornelis Ozinga
Original Assignee
Dsm N.V.
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
Priority claimed from EP00204162A external-priority patent/EP1209199A1/fr
Priority claimed from EP01202116A external-priority patent/EP1262522A1/fr
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU2002221197A priority Critical patent/AU2002221197A1/en
Publication of WO2002042373A1 publication Critical patent/WO2002042373A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
    • B29C70/021—Combinations of fibrous reinforcement and non-fibrous material
    • B29C70/025—Combinations of fibrous reinforcement and non-fibrous material with particular filler
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/18—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length in the form of a mat, e.g. sheet moulding compound [SMC]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • B44C5/0453—Ornamental plaques, e.g. decorative panels, decorative veneers produced by processes involving moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F9/00—Designs imitating natural patterns
    • B44F9/04—Designs imitating natural patterns of stone surfaces, e.g. marble
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Definitions

  • the invention relates to a granite-look reinforced laminar product comprising fibrous material, grinded coloured (semi)cured aminoplast resin based granules and a thermosetting aminoplast resin mixture as matrix brought together between supporting sheets.
  • the invention also relates to a sheet moulding compound (SMC) production process for manufacturing such product and to moulded parts prepared therefrom.
  • aminoplast comprises the condensation products of amino compounds and an aldehyde.
  • the amino compounds in aminoplasts are usually selected from the groups of urea and its derivatives, and of triazines and derivatives thereof, e.g. triamino-S-triazine (also known as melamine).
  • the melamine-aldehyde i.e.
  • melamine-formaldehyde condensation product is hereinafter also referred to as MF.
  • MF melamine-formaldehyde condensation product
  • combinations of urea and melamine aldehyde condensation products can be used. These can be referred to as MUF.
  • the term (semi)cured includes fully cured and partially cured aminoplast resin based granules with a rest enthalpy ⁇ 60%, preferably ⁇ 40% of the rest enthalpy of uncured aminoplast resin based granules. Fully cured aminoplast resin based granules have a rest enthalpy ⁇ 20% of the rest enthalpy of uncured aminoplast resin based granules. For instance for MF, the rest enthalpy of uncured aminoplast resin based granules is about 50 J/g (as measured with differential scanning calorimetrie, DSC).
  • JP-A- 07,016,850 an artificial stone-like decorative panel is described which is made of (i) a decorative layer comprising a thermosetting resin mixture, in particular a MF resin or an unsaturated polyester resin or a combination of these two, a granular colouring agent, in particular broken kernels of a coloured thermosetting resin mixture with a particle diameter size of 300 ⁇ m to 5 mm, and a filler, and (ii) a base layer which is laminated to the decorative layer, comprising a thermosetting resin impregnated glass-fibre chopped-strand mat.
  • a thermosetting resin mixture in particular a MF resin or an unsaturated polyester resin or a combination of these two
  • a granular colouring agent in particular broken kernels of a coloured thermosetting resin mixture with a particle diameter size of 300 ⁇ m to 5 mm
  • a base layer which is laminated to the decorative layer, comprising a thermosetting resin impregnated glass-fibre chopped-strand mat.
  • the glass-fibre mat is put on the decorative layer and that the thermosetting resin impregnates the glass-fibre mat.
  • the production of artificial stone-like decorative panels from such laminar products takes place in a mould of which the inner walls have been pre-treated with a mould release agent (e.g. wax, silicone resin or aqueous PVA solution).
  • a mould release agent e.g. wax, silicone resin or aqueous PVA solution.
  • the laminar product is put in the mould and vibrated for 1 minute so that the base layer is laminated on the decorative layer.
  • the granite-look laminar product is then first hardened for 2 hours at a temperature of 30°C then removed from the mould and post-cured for 2 hours in a furnace at 100°C.
  • JP-A-07,016,850 is not suitable for production of artificial granite-look products with a perfectly flat surface, because the lamination of two layers consisting, of different materials easily results in cured products with a warped surface.
  • Warping of a surface is the phenomenon that the surface of a cured product is not totally flat, but is buckled or distorted.
  • the first object of the present invention is to overcome the still existing need for providing granite-look reinforced laminar products which do not exhibit the abovementioned problems and which can easily be moulded to products with sufficient strength and granite-look appearance throughout the final product.
  • Another object of the present invention is to provide a granite-look reinforced laminar product with homogenously 3D distributed coloured granules in the resin mixture as matrix.
  • Another object of the present invention is to provide a granite-look reinforced laminar product that has no warped surface upon curing and is not susceptible for staining.
  • Another object of the present invention is to provide an improved, cost-efficient and quicker process for producing granite-look laminar products comprising a thermosetting aminoplast resin mixture as matrix, grinded coloured (semi)cured aminoplast resin based granules and fibrous material which does not have the abovementioned disadvantages.
  • the granite-look reinforced laminar product comprising fibrous material, grinded coloured (semi)cured aminoplast resin based granules and a thermosetting aminoplast resin mixture as matrix
  • a removable first carrier sheet and a removable second carrier sheet between which two sheets a compound consisting of (a) 1 to 25 wt.% of grinded coloured (semi)cured aminoplast resin based granules and
  • thermosetting aminoplast resin and the grinded coloured (semi)cured aminoplast resin based granules in the granite-look laminar product according to the invention can, in principle, be any aminoplast resin (as is obtained by condensation of an amino compound and an aldehyde), particularly any aminoplastic (form)aldehyde resin.
  • examples of such resins are those that contain urea or melamine as amino compound; also MUF combinations may be used.
  • a melamine-aldehyde is used, because of its superior mechanical, surface and flame-resistant properties. The capability of pigmentation is also improved further.
  • the advantages of the products according to the invention are manifested, in particular, if the thermosetting resin is an MF resin.
  • the aminoplast resin can be manufactured in a manner known to the person skilled in the art by reacting an amino compound and formaldehyde in water.
  • the ratio of, for example, formaldehyde and melamine is, normally speaking, between 1.0 and 2.5, preferably between 1.1 and 2.0.
  • plasticizers such as, for example, sorbitol, ⁇ -caprolactam, ethylene glycol, trioxitol, toluenesulphonamide and products from the family of guanamines (benzo-, aceto- and diguanamines).
  • the loss on cure is less than 10 wt.% of the total weight of the granite-look laminar product.
  • This percentage of loss on cure can easily be achieved by drying the laminar product in its production process before any of the first and/or second carrier sheets have been removed.
  • the loss on cure as used in this application is determined by percentage of weight loss (e.g. free moisture, water and/or other volatiles) when the granite-look laminar product is dried in a ventilation oven at 160°C for 0.5 hours.
  • the granite-look laminar products according to the invention are suitable for being dried between the carrier sheets to lower the loss- on-cure value, direct processing in closed moulds is possible afterwards, upon removal of any of the carrier sheets, without problems of foaming, blistering and porosities in the final product.
  • the aminoplast resin mixture present in the granite-look laminar product consists of filler and/or other additive materials.
  • This resin mixture may contain all kinds of fillers.
  • Said fillers can be the same as the conventional fillers for granite-look laminar products based on, for example, unsaturated polyester resins.
  • lime, calcium carbonate, clay, carbon particles, silica, aluminium trihydrate, quartz and/or metal particles can be used as fillers.
  • the resin mixture contains aluminium trihydrate and/or calcium carbonate as filler.
  • the granite-look laminar product may also contain catalysts, mould release agents, pigments, dispersion agents and other conventional additives.
  • the grinded coloured (semi)cured aminoplast resin based granules can be manufactured in a manner known to the person skilled in the art by crushing coloured (semi)cured aminoplast resin plates or (reinforced)SMC's. Different fractions of grinded coloured (semi)cured aminoplast resin based granules, obtainable by sieving, and characterised by different diameter ranges of the granules, can be used in the production of the granite-look laminar products.
  • All pigments that are compatible with the aminoplast resin can be used for colouring the (semi)cured aminoplast resin based granules.
  • Separately produced charges of (differently coloured; at least two colours) granules may be mixed.
  • the density of the granules can be chosen between 1 gr/cm 3 and 2.5 gr/cm 3 . This extremely broad suitable range is advantageous and it is impossible that such broad range is used in any of the hitherto known laminar products. Suitable granules in the lower density range 1 -1.5 gr/cm 3 can be obtained e.g.
  • the diameter range of the granules is not very critical.
  • the diameter of the granules is usually in the range of from about 0.1 to 1.0 mm, preferably 0.3 to 0.7 mm.
  • the granules are being homogeneously 3D distributed in the resin mixture as matrix. As used herein, homogeneously 3D means that the granules are distributed throughout the whole resin matrix. In practice this can be easily achieved by mixing the granules directly in the resin mixture by using a mixer.
  • the coloured (semi)cured aminoplast resin based granules preferably have a good compatibility with the thermosetting aminoplast resin mixture.
  • granite-look laminar products are produced which, upon curing, result in plates having a nice granite-look appearance and a very smooth surface which does not exhibit warping and is not susceptible for staining.
  • Warping is the phenomenon that plates tend to distort from their flat surface.
  • Staining is a phenomenon that various liquids, when left or spoilt at a surface, leave flecks or spots penetrating into such surface.
  • the fibrous material may be inorganic fibres (natural and/or synthetic), e.g. mineral fibres, but also organic fibres (natural and/or synthetic) may be used as part of the fibrous material.
  • Suitable fibres are, for example, carbon fibres, glass fibres, rock fibres, cotton-wool fibres, fibres based on highly oriented thermoplastics, such as aramids and UHMWPE (ultra-high molecular weight polyethylene) fibres, polyamide fibres and cellulose fibres.
  • Particularly suitable fibres are glass fibres.
  • At least 60 wt.% of the fibrous material consists of chopped fibres having an average length in the range of from 10 to 100 mm.
  • the chopped fibres being substantially 2D-randomly distributed in the compound between two layers of said resin matrix with homogeneously 3D distributed granules ((a)+(b)).
  • substantially 2D-randomly distributed means that the chopped fibres are more or less evenly, in random orientations, distributed in a plane which can be considered to be about parallel to the planes of the first and second removable carrier sheets (or the upper and lower planes of the granite-look laminar product after removal of those sheets).
  • this can be easily achieved by distributing the chopped fibres directly from a chopping unit onto a first layer of resin mixture matrix and granules supported on the first carrier sheet and applying on top thereof a second layer of resin mixture matrix and granules supported by the second carrier sheet, thereby making a sandwich which may be even better homogenized by passing the granite-look laminar product through a series of rollers so that the fibrous material is thoroughly impregnated and the granules are homogeneous distributed, as in standard SMC processes.
  • the granite- look reinforced laminar product contains at least 14 wt.% of fibrous material, and at least 60 wt.% thereof consists of chopped fibres.
  • the fibrous material also contains cellulose fibres, in an amount of from about 5.5 to 9.5 wt.% of the resin mixture as matrix.
  • the cellulose fibrous material is already, homogeneously distributed, present in the thermosetting aminoplast resin mixture before the chopped fibres are being distributed therein.
  • any type of cellulose may be used, for instance single cellulose pulp fibres, but crystalline cellulose is most preferred.
  • the cellulose containing materials are least susceptible to staining, and, moreover, are very favourable as to scratch resistance and Taber abrasion test.
  • Scratch resistance may be determined as is also described in DIN 53799 and ISO 4586, by stepwise increasing the scratching force from 1.0 N to 5.0 N (in 0.5 N steps).
  • the Taber abrasion test which is also described in DIN 53799 and ISO 4586, the weight loss of a sample is determined after 500 revolutions with sanding paper (renewed after each 100 revolutions).
  • the cellulose fibrous material is preferably pre-treated by impregnation, for instance with dimethylol melamine, to reduce water absorption.
  • the aminoplast resin mixture and/or the granules in the laminar products according to the invention are composed of a melamine- aldehyde resin.
  • the granite-look laminar product according to the invention has a loss on cure in the range of 0.5 to 10 wt.% of the total weight of the granite-look laminar product, preferably in the range of from 1.0 to 8 wt.% and most preferably in the range of from 2.0 to 4.0 wt.%.
  • the moulded end products obtained have a completely homogeneous appearance and are porosity-free, thereby being insusceptible for staining. If the granite-look laminar product has a loss on cure of less than 0.5 wt.%, flow moulding thereof is not feasible.
  • the lowering of the percentage loss on cure can be obtained by drying the granite-look laminar product without removal of any of the carrier sheets.
  • the drying may be performed most conveniently if a proper choice of carrier sheets is made.
  • the removable first and/or second carrier sheets in the laminar products according to the invention therefore preferably have a permeability for water vapour at 23°C of 10 g/m » day or more, preferably 25 g/m 2» day or more as determined according to DIN 53122. This permeability for water vapour is especially important during the production process for the granite- look laminar products.
  • the skilled man will be readily able to find which carrier sheets are suitable for being applied according to the invention. Many types of suitable carrier sheets are commercially available and their properties, e.g.
  • the two carrier sheets (films) on the granite-look laminar products will prevent contamination of the granite-look laminar product during production, handling and transport. This will enable the granite-look laminar products to be applied in such market segments where the outer appearance of the final products is critical.
  • the granite-look laminar products according to the invention preferably at least two fractions of the granules, with each different diameter ranges, are being used to get a product with a deeper and more complex pattern.
  • a mixture of granules with at least two different colours is being used.
  • the chopped fibrous material in the granite-look laminar product according to the invention preferably consists of chopped glass fibres having an average length in the range of from 12 to 60 mm. It can, however, also be advantageous that part of the fibrous material used in the granite-look laminar products according to the invention consists of continuous fibres (rovings). Such continuous fibres, particularly when they are present in the granite-look laminar product unidirectionally and in appropriate amounts, may provide to the product additionally improved mechanical properties in specific directions. Also in these embodiments of the invention part of the fibrous material may be replaced by cellulose, taking into account that still at least 60 wt.% of the fibrous material consist of chopped fibres.
  • the fibrous material in the granite-look laminar product according to the invention consists of glass fibres and contains less than 1 wt.% of sizing and binder material as determined by the loss-on-ignition test. In such case granite-look laminar products with best homogeneity and outer appearance are being obtained.
  • the granite-look laminar products according to the invention have a loss on cure of less than 10 wt.% and can be used in closed mould techniques. They also can be used for the production of homogeneous, relatively thick materials, whereas the granite-look laminar products according to the prior art are only suitable for production of relatively thin materials or - in case of production of thicker materials - are only being used as a top-layer attached to a backing.
  • the invention also relates to a novel (SMC-)process for • manufacturing granite-look reinforced laminar products comprising fibrous material, grinded coloured (semi)cured aminoplast resin based granules and a thermosetting aminoplast resin mixture as matrix.
  • This new process comprises the steps of i) mixing grinded coloured (semi)cured aminoplast resin based granules (a) having a density of between 1 gr/cm 3 and 2.5 gr/cm 3 in an aminoplast resin mixture (b) as a matrix of which resin mixture 20 to 90 wt.% consists of filler and/or other additive materials and which resin mixture has a viscosity in the range of from 5 to 250 Pa » s, preferably of from 20 to 100 Pa » s, to get a mixture of (a) and (b) wherein (a) is being homogeneously 3D distributed in (b); ii) applying a part of the mixture of (a) and (b) to a removable first carrier sheet and applying another part of the mixture to a second removable carrier sheet thereby obtaining two layers of supported mixture to be used as a lower layer and an upper layer between which iii) fibrous material (c) of which at least 60 wt.% of the fibrous material consists of chopped fibres having
  • resin mixture (b) vs. fibrous material (c) are respectively 1 to 25 wt.% vs. 20 to 90 wt.% vs. 5-35 wt.% (all percentages indicating the solid material contents of the starting materials, and the total of the percentages in (a), (b) and (c) adding up to 100 wt.%) iv) and drying said sheet moulding compound, without removal of any of the carrier sheets, to a loss on cure of less than 10 wt.%.
  • thermosetting aminoplast resin and the grinded coloured (semi)cured aminoplast resin based granules used in the process according to the invention can, in principle, be any aminoplast resin (as is obtained by condensation of an amino compound and an aldehyde), particularly any aminoplastic (form)aldehyde resin.
  • aminoplast resin mixture and/or granules can also be prepared from solid aminoplast materials, for instance from spray-dried resin, by adding - at an elevated temperature, e.g.
  • the diameter range of the granules used is not very critical.
  • the diameter of the granules is usually in the range of from about 0.1 to 1.0 mm, preferably 0.3 to 0.7 mm.
  • the aminoplast resin mixture preferably is filtered before or after the addition of the grinded coloured (semi)cured aminoplast resin based granules to remove undesirable sedimentations from the resin mixture.
  • the filter should have a larger mesh size, so that the granules can pass the filter and the sedimentation stay on the filter. It may be advantageous to add a viscosity adjuster (e.g. Versa TL) to improve the filterability.
  • the viscosity of the resin mixture used in this process should be chosen between 5 and 250 Pa » s, preferably even between 20 and 100 Pa » s. This viscosity is considerably higher than the viscosity of that of resin mixtures used in the impregnation of non-woven mats in techniques of the prior art, for instance as described in EP-A-845,346.
  • the granules are being dispersed better and more homogeneously 3D in the resin mixture. This leads to less sedimentation of the granules in the granite-look laminar products. Also the surface of the final cured moulded products is not susceptible for staining.
  • aminoplast resin mixture and/or the granules used in the process according to the invention are composed of a melamine-aldehyde resin.
  • the sheet-moulding compound is preferably dried to a loss on cure in the range of from 0.5 to 10 wt.% of the total weight of the granite-look laminar product, preferably in the range of from 1.0 to 8 wt.% and most preferably in the range of from 2.0 to 4.0 wt.%.
  • the granite-look laminar product, before being dried is pre-cut according to desired dimensions, for instance, equal to the inlay pattern for the mould used. The pre-cutting before drying prevents the occurrence of bare glass fibres at the cutting edges.
  • a loss on cure of less than 10 wt.%, particularly in the ranges as mentioned above, has been found to give good results.
  • Too high loss-on-cure values may result in pores, blisters, whitening (colour fading) and other defects in the final product upon curing, which also adversely affects the mechanical properties.
  • the drying can easily be achieved, for instance, in an oven through which the sheet-moulding compound is transported, without removing the carrier sheets. Also drying off-line, at relatively low temperature, for instance at ambient temperature or even up to about 100°C, in drying chambers is possible. The latter embodiments of drying may be performed while storing the SMC's until the loss on cure has reached a desired value.
  • drying process is rather quick, especially when spacers are being used between the separate SMC's, for instance, by separating the SMC's by individual layers of corrugated cardboard or otherwise, low loss-on-cure values are being reached already within a few days at 60°C. Drying in an oven, of course, is quicker. The drying may also be assisted by vacuum.
  • Part of the drying also can be achieved by the presence, in the aminoplast resin mixture matrix, of desiccants or of products like gypsum and/or cement.
  • Such additives have a function different from that of conventional thickening agents, which are mainly being used for influencing the viscosity of the sheet moulding compounds. This way of (internal) drying, however, does not lead to a weight decrease of the granite-look laminar product, but merely to lowering the content of free moisture in the compound.
  • the chopped fibrous material as used in the process according to the invention, consists of glass roving having an average length in the range of from 12 to 60 mm.
  • the chopped fibrous material preferably has strand tex numbers in the range of from 18 to 300 tex, especially preferred in the range of from 35 to 100 tex.
  • continuous fibres are being distributed and impregnated in the resin mixture matrix with the granules, together with and in the same plane as the chopped fibres.
  • the content of chopped fibrous material in the granite-look laminar product according to the invention may be controlled by the chopper speed.
  • the granite-look reinforced laminar product contains at least 14 wt.% of fibrous material, and at least 60 wt.% thereof consists of chopped fibres.
  • part of the fibrous material is replaced by cellulose fibres, in an amount of from about 5.5 to 9.5 wt.% of the resin mixture as matrix.
  • the cellulose fibres preferably already are homogeneously mixed into the resin before the chopped fibres are being added thereto.
  • cellulose fibrous material any type of cellulose may be used, for instance single cellulose pulp fibres, but crystalline cellulose is most preferred.
  • the cellulose fibrous material is preferably pre-treated by impregnation, for instance with dimethylol melamine, to reduce water absorption.
  • the fibrous material used consists of glass fibres and contains less than 1 wt.% of sizing and binder material, as determined by a loss-on-ignition test. In such case granite-look laminar products with best homogeneity and outer appearance are being obtained.
  • the removable first and/or second carrier sheets preferably have permeability for water vapour at 23°C of 10 g/m 2 »day or more, preferably 25 g/m 2, day or more, as determined according to DIN 53122.
  • the process can be performed more consistently, i.e. the properties of the products obtained show less variations over subsequent production runs;
  • the granite-look laminar products made according to the invention can conveniently be used, upon removal of the first and second carrier sheets, in closed mould processes, e.g. for flow moulding.
  • the inlay pattern usually will be equal to the dimensions of the moulding part (100% inlay).
  • the pressure used in such flow moulding processes is usually between 1 and 20 MPa (between about 10 and 200 bar), preferably between 5 and 10 MPa (between about 50 and 100 bar).
  • the usual moulding temperature, which also ensures the curing of the thermosetting resin, is between 50 and 200°C, preferably between 140 and 170°C.
  • the present invention therefore also relates to use of the granite-look laminar products according to the invention or obtained through a process according to the invention, upon removal of the first and second carrier sheets, in a closed mould production process.
  • the invention also relates to moulded products obtained in a closed mould process with the aid of a granite-look laminar product according to the invention or obtained through a process according to the invention.
  • the granite-look laminar products according to the invention products obtained have better isotropic properties than the products of the state of the art and, as a result, there are no problems of warping, susceptibility for staining, insufficient scratch resistance, Taber abrasion, etc. which often occur in moulded products produced differently.
  • It is an additional advantage of the granite-look laminar products according to the invention that mechanical properties are obtained which are in the same range as for products of the prior art, but at a lower content of fibrous material in the product.
  • the granite-look laminar products can be used particularly satisfactorily in the manufacture of moulded parts, for example bodywork components for lorries and cars.
  • Particularly suitable applications are wall panels in trains and public transport (including aircraft), wall claddings for indoor or outdoor use, as well as kitchen and sanitary appliances, such as oven doors, worktops, trays and the like.
  • the particularly good fire-resistant properties, heat resistance, high-temperature dimensional stability, scratch resistance, stain resistance and granite-look appearance are of great advantage.
  • caprolactam 5 parts of caprolactam, 24 parts of water and 135 parts of formalin (30% formaldehyde in water having a pH of 9.4) were added to 100 parts of melamine.
  • the condensation reaction was carried out at 95°C until the dilution capability (water tolerance) at 20°C of the resin was 1.2 kg of resin per kg of water.
  • the formaldehyde/melamine ratio was 1.7.
  • the viscosity of the resin is about 1800 mPa « s.
  • the solid content of the resin matrix is about 66.8 wt.%
  • Coloured (semi)cured MF resin plates are grinded and sieved to get different fractions of granules of different diameter ranges.
  • the particle size of the grinded granules is, for instance, in the range of from 100 to 1000 ⁇ m.
  • Mixtures of differently coloured granules for instance, black coloured granules/white coloured granules in a ratio of 1 :3 (wt./wt.) were made, as well as mixtures of granules of different diameter ranges.
  • a 1 :1 (wt./wt.) mixture of the above prepared wet MF resin and spray dried MF-resin (Madurit from Vianova Resins Germany) is filtered over a filter with 1 mm diameter sieve opening to obtain a resin mixture matrix (solid content about 83.4 wt.%).
  • resin mixture 1 B (resin matrix + granules + cellulose)
  • a 1 :1 (wt./wt.) mixture of the above prepared wet MF resin and spray dried MF-resin (Madurit from Vianova Resins Germany) is filtered over a filter with 1mm diameter sieve opening to obtain a resin mixture matrix (solid content about 83.4 wt.%).
  • resin mixture 2 (resin matrix + granules)
  • the resin mixture 1 A, 1 B or 2 was transferred to two doctor boxes of a standard SMC line.
  • the resin mixture was added on two carrier sheets (upper and lower, respectively).
  • carrier sheets a polyamide film (Rodethul mono Yellow, from Eurozak, Diest, Belgium) were used. Chopped fibrous material is put on the lower carrier sheet in an amount of 1/5 wt./wt. of the compound (solid content).
  • the upper and lower carrier sheets with the resin mixture and fibrous material were brought together as a sandwich. Impregnation of the fibrous material occurred in the compaction zone.
  • the granite-look laminar product so obtained was dried, without removal of any of the carrier sheets, in either of two ways:
  • Drying of the material to the required loss on cure of 8 wt.% (for resin mixtures 1 A and 1 B) or 4 wt.% (for resin mixture 2) took respectively about 200 hours at 30°C; about 100 hours at 45°C and about 50 hours at 60°C.
  • the consistency of the granite-look laminar products obtained in both ways of drying was judged as being excellent.
  • the surface weight turned out to be 3300 ⁇ 50 g/m 2 for resin mixture 1 A, 3250 ⁇ 50 g/m 2 for resin mixtures 1 B and 3100 ⁇ 50 g/m 2 for resin mixture 2.

Abstract

L'invention concerne des produits laminaires renforcés d'aspect granité comprenant une matière fibreuse, des granules en couleur, broyés et (semi)durcis, à base de résine aminoplaste thermodurcissable, et un mélange de résine aminoplaste en tant que matrice. Ce produit laminaire, qui présente une perte en traitement inférieure à 10 % en poids, contient, placé entre deux feuilles de transport amovibles, un composé constitué de : (a) entre 1 et 25 % en poids de granules en couleur, broyés et (semi)durcis, à base de résine aminoplaste thermodurcissable (ayant une certaine densité et étant répartis en 3D dans la matrice); (b) entre 20 et 90 % en poids d'une charge contenant un mélange de résine aminoplaste; et (c) entre 5 et 35 % en poids de matière fibreuse, dont au moins 60 % est coupée, (répartie aléatoirement en 2D dans le composé entre deux couches de ladite matrice de mélange de résine), tous les pourcentages indiquant les taux de matière solide des matières premières, et le total des pourcentages dans (a), (b) et (c) s'additionnant jusqu'à atteindre 100 % en poids. L'invention concerne également un procédé de production de préimprégné (SMC) servant à fabriquer lesdits produits ainsi que des parties moulées préparées à partir desdits produits.
PCT/NL2001/000807 2000-11-23 2001-11-07 Produit laminaire renforce d'aspect granite a base d'aminoplaste thermodurcissable WO2002042373A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002221197A AU2002221197A1 (en) 2000-11-23 2001-11-07 Granite-look reinforced laminar product of a thermosetting aminoplast

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00204162.2 2000-11-23
EP00204162A EP1209199A1 (fr) 2000-11-23 2000-11-23 Produit laminaire en mélange de résine aminoplaste renforcée à l'aspect granité
EP01202116.8 2001-06-01
EP01202116A EP1262522A1 (fr) 2001-06-01 2001-06-01 Laminaire renforcé d'un mélange de résine aminoplaste thermodurcissable à l'aspect de granite

Publications (1)

Publication Number Publication Date
WO2002042373A1 true WO2002042373A1 (fr) 2002-05-30

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Country Status (2)

Country Link
AU (1) AU2002221197A1 (fr)
WO (1) WO2002042373A1 (fr)

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