NL1011468C2 - Sheet-shaped prepreg. - Google Patents

Description

- 1 -

SHAPED PREPREG

The invention relates to a sheet-shaped prepreg containing one or more layers of a sheet-shaped support, which support is impregnated with an as yet uncured resin.

Sheet-like prepregs containing multiple alpha-cellulose supports stacked on top of each other, impregnated with the reaction product of formaldehyde and melamine, are known, for example, from US-A-3730828. According to this patent, paper is first impregnated with a melamine-formaldehyde resin.

A prepreg is then made by drying a few layers of this impregnated paper and placing them on top of each other. For example, under a pressure of 6 MPa and at a temperature of about 150 ° C, the resin is cured in a press to yield a sheet-like product. The reaction between formaldehyde and melamine in the sheet-like product thus obtained is complete at the temperature used (completely cured). The sheet-like articles described in the aforementioned patent 25 appear to have good postforming properties.

By postforming it is meant here that the sheet-shaped article can be bent at an elevated temperature which lies between 160 and 180 ° C. It is hereby possible to bend the sheet-shaped article 30 somewhat along one axis (the so-called 2D-deformation whereby 2D shaped parts are obtained), without the sheet-shaped article breaking and / or tearing.

101 1 4 r) c - - 2 -

A drawback is that starting from a prepreg according to US-A-3730828 it is not possible to obtain sheet-shaped products which can be bent along two (or more) intersecting axes into complex shapes without breaking or tearing (the so-called 3D -forming in which 3D shaped parts are obtained). With complex shapes you can think for example of a saddle-shaped pattern, a tub, a hemisphere, a sickle pattern or a pimple.

The object of this invention is to provide a prepreg with which complex shapes can be obtained and / or covered.

This object is achieved with a prepreg containing one or more layers of a sheet-like porous support, which sheet-like porous support is impregnated with an as yet uncured resin, the support containing a fusible polymer mixed with cellulose or regenerated cellulose or mixtures or combinations thereof. The ratio between fusible polymer and cellulose or regenerated cellulose is determined by the final application and can vary between very wide limits. For example, the fusible polymer content can be between 1 and 99% by weight. As cellulose, wood or paper pulp is preferably used, more in particular kraft paper pulp. Regenerated cellulose means treated cellulose. This treatment means that cellulose is converted into a soluble cellulose derivative (usually the xantagonate), this derivative is, for example, converted into fibers via a spinning process, after which these fibers are converted into regenerated 1011 468-3 cellulose fibers using an acid. For example, a woven or non-woven porous support can be manufactured from these regenerated cellulose fibers.

Preferably, a cellulose acetate is used as the meltable polymer 5. By a cellulose acetate-containing carrier is meant a carrier containing cellulose acetate of which between 0.01-3 (degree of substitution) of the OH groups of the monomer units are acetylated such as cellulose monoacetate, cellulose diacetate, cellulose triacetate as well as mixtures or combinations of these acetates. Preferably, the degree of substitution is between 2 and 3.

The cellulose acetate-based carrier may also contain a plasticizer. If a plasticizer is used, this plasticizer can be spun together with the cellulose acetate into fibers, after which these fibers can be converted into a plasticizer-containing carrier. Also, cellulose acetate fibers can be treated with plasticizer and then converted into a plasticizer-containing carrier. A third possibility is to subsequently treat the cellulose acetate-containing carrier with plasticizer. All plasticizers known for cellulose acetates can be used as plasticizers, such as, for example, triacetin, triethyl citrate, diethyl citrate, N-methyl-o, p-toluenesulfonamide, phosphates and phthalates, in particular diethyl phthalate. The advantage of adding a plasticizer is that the glass transition temperature of the cellulose acetate support can be controlled.

101 1468 - 4 -

The elongation at break of the individual sheet-shaped porous support and of the resulting prepreg is greater than 2%, preferably greater than 5% and especially greater than 10%. The elongation at break is hereby measured at a temperature substantially equal to the temperature at which the carrier or prepreg is processed into sheet-like product.

It has been found that, based on the prepreg according to the invention, sheet-shaped products 10 can be made in the most diverse shapes without cracks being formed in the sheet-shaped product during deformation.

Sheet shaped articles with shapes in which the prepregs are stretched locally during molding from 10% to over 400% are now possible.

Articles where the required maximum deformation is less than 10% can also be coated better with the sheet-shaped article according to the invention than with sheet-based paper-based articles. Examples are some so-called 'softline' panels, 3d-shaped panels with round edges and / or corners, and / or gradually sloping surfaces or contours.

A further advantage is that the further curing of the resin and the deformation can be carried out in one step. This is in contrast to the method described in the aforementioned US-A-3730828 where, from the prepreg, two steps are required to arrive at a formed end product.

An additional advantage is that the prepreg can be processed with a variety of techniques, 101 1 468 - 5 - so that the most optimal technique can always be applied per end product.

Another advantage is that, based on the prepregs according to the invention, both 2D and 3D-5 objects can be coated, making it possible to obtain an identical decor on both objects, for example the decor of a 3D kitchen cabinet and a 2D laminate floor.

Starting from the prepreg according to the invention it is furthermore possible to make sheet-shaped products which, for instance along one axis, are bent to an acute angle. This is not possible on the basis of the known prepregs based on a paper carrier.

JP-A-7002119 discloses a prepreg consisting of a carrier of a polyamide non-woven material and a carrier of kraft paper, which carriers are individually impregnated with a melamine-formaldehyde resin and then stacked. An impregnated polyamide non-woven backing generally has an elongation at break of more than 2%. However, impregnated kraft paper has an elongation at break of less than 2%, making the elongation at break of the prepreg as a whole less than 2%.

A sheet-like porous, meltable polymer-containing polymeric carrier is understood to mean any polymeric carrier which has a high degree of porosity. The porosity of the polymeric carrier is essential to obtain the advantageous properties of the prepreg as described above. Due to the high porosity, the sheet-shaped 101 1468-6 polymer carrier can be homogeneously filled with the resin. Preferably, the porosity is obtained in the form of microscopically interconnected cavities and preferably slightly larger cavities and holes are present. Larger cavities and holes lead to loss of resin during further processing of the prepreg to its final shape. Preferably, the porosity is sufficiently large that at least 30% by volume of the final molded article consists of resin.

The porous polymeric fusible polymeric carrier will preferably be a woven or nonwoven sheet polymer, a sheet open polymer foam or a microporous membrane. Preferably, the fibers of the non-woven have a diameter of less than 0.1 mm. Non-woven fabrics with very small diameter fibers are also called open films. Due to the small wire diameter, this class of nonwovens has few larger meshes and many microscopically small interconnecting cavities. Foams of 20 polymers have interconnected voids. The cavities preferably have a diameter of less than 1 mm. Occasionally larger cavities may be present in the foam if more than 80% by volume of the cavities have these smaller diameters.

For example, the porous cellulose acetate-containing polymeric carrier can be prepared by pouring a solution of a cellulose acetate in acetone into stirred ethanol. This produces fibers of a cellulose acetate. The length and diameter of these fibers can be influenced by, among other things, changing the concentration of the cellulose acetate in acetone or adjusting the stirring speed during the addition of the cellulose solution to the ethanol. The resulting fibers of a cellulose acetate can then be added to paper pulp and converted into a porous cellulose acetate-containing paper carrier in a known manner.

Another method of preparation is to convert a cellulose acetate solution into acetone via a spinning head into filaments of cellulose acetate, whereby the acetone evaporates. Chopping the threads and adding to paper pulp after work-up yields a porous cellulose acetate-containing paper support.

Instead of chopping the threads into pieces, it is also possible to convert the threads in known manner into wovens and non-wovens and to use them as a porous support.

It is also possible to add cellulose acetate fibers instead of kraft pulp to commercially available fully or partially regenerated celluloses. These regenerated celluloses are known, inter alia, under the generic names viscose and rayon or under the brand name Lyocell® (a product of Acordis). Fully or partially regenerated celluloses are prepared by modifying and solubilizing cellulose, which is the major constituent of wood pulp, among others, by making it a cellulose xantagonate, for example.

These cellulose xantagonates, in contrast to cellulose itself, are soluble and spinnable, so that 30 threads can be obtained. These threads can be regenerated in an acid medium to yield threads of 101 1468-8 regenerated cellulose. These threads can then be converted into fibers and added, for example, to paper pulp or converted into a web such as a woven or non-woven.

The porous polymeric carrier can in principle be any porous polymeric carrier which contains a fusible polymer and which satisfies the requirement that the impregnated carrier has an elongation at break, measured at the processing conditions, of more than 2%. Porous carriers such as wovens or non-wovens can for instance be manufactured from the cellulose acetates already mentioned, but also from, for example, polyethylene; polypropylene; polystyrene; ethylene propylene copolymers; EPDM; polyamides such as, for example, nylon 6,6 or nylon-15 6; ethyl cellulose, SMA / SAN; polyesters such as, for example, polyethylene terephthalate (PET) or polybutene terephthalate (PBT); polyethers or folks thereof. The above-mentioned polymers can be used as a woven or non-woven, open film or as an open polymer foam as a porous polymeric support.

The wearer may have both polar and non-polar properties. By using suitable wetting agents, the desired degree of impregnation of the polymer sheet by the resin 25 can be obtained. As a rule, all wetting agents known to those skilled in the art can be used.

Examples of wetting agents are PAT® 523W, PAT® 959 (PAT® is a brand name of Würtz), Nonidet® P40 (Nonidet® P40 is a brand name of Sigma Chemie) and 30 Aminol® N (Aminol® is a brand name of Chem-Y ).

The resin with which the support is impregnated can in principle be any known resin and may additionally contain a reactive or non-reactive solvent. The resin can also consist of polymerizable monomers. Examples are thermosetting resins or elastomeric resins, which resins can be cured via an ionic, radical, oxidation, addition or condensation mechanism or via a combination of these mechanisms, for example in the so-called 'dual-cure' curing.

Examples of resins which cure via an oxidation mechanism are alkyd resins. Usually, however, cationic and / or radically curable resins are used and / or resins which cure through a condensation or addition reaction.

Cationic or radically curable resins can cure by a homopolymerization or a copolymerization reaction. Radically curable resins may contain unsaturated monomers and / or groups including (meth) acrylate, itaconate, maleate, fumarate, styrene, fumaramide, maleamide, maleimide, vinyl ether, allyl ether and / or vinyl ester groups. Examples of this are the acrylate resins.

Cationic curing resins may contain monomers and / or groups containing polymerisable groups such as, for example, epoxy, glycidyl, cycloaliphatic epoxide, vinyl ether, vinyl ester, allyl ether, allyl ester, propenyl ether, butenyl ether, vinyl acetate, oxetane. , cyclic carbonate and / or dioxalane groups. Examples of these are epoxy resins.

Resins which cure via an addition or condensation mechanism are, for example, aminoplast resins, phenol formaldehyde resins (PF resins) 101 1468 - 10 and / or two-component resins consisting of hydroxyl-functional polymers or oligomers and isocyanate-functional oligomers or polymers and / or alkylated melamine resins.

Preferably, an aminoplast resin is used. As an aminoplast, compounds of formaldehyde with, for example, urea, melamine, acetoguanamine or benzoguanamine can be used, or mixtures or combinations thereof. Preferably melamine is used because of superior mechanical properties of the end product. The aminoplast resin can be manufactured in a method known to the person skilled in the art by reacting, for example, melamine and / or urea with formaldehyde in water. Optionally, the urea and / or the melamine can be partly replaced by, for example, phenol, but this can have negative effects on the color. Modifiers can also be added, such as sorbitol, ε-caprolactam, ethylene glycol, polyethylene glycol, polypropylene glycol, hydroxy functional polyesters, hydroxy functional acrylates, trioxitol, toluenesulfonamide, and benzo and acetoguanamine.

Mixtures or combinations of resins which can be cured by various mechanisms, such as for instance a mixture of a melamine-formaldehyde resin and an acrylate-functional resin, can be used to impregnate the carrier. These resins may be prepared and / or cured in the presence of a catalyst and / or initiator specific to each resin system, as is known to those skilled in the art.

Practically useful mechanical properties of 101 146 8-11 are achieved if 10-70 wt.% Porous polymer and 90-30 wt.% Resin are used. The resin can contain the known pigments, dyes and / or fillers as known, for example, from the paper industry. Examples include titanium dioxide, iron oxide, clay, glass, lime, carbon, silica or metal particles. However, it has been found that the best results are achieved in the absence of fillers or at least with fewer fillers than has hitherto been customary. The weight ratio of fillers and resin is preferably between 0: 1 and 0.5: 1. These ratios relate to the cured final sheet-shaped article.

The prepreg is made under the conditions already known for making paper carrier prepregs, as described, for example, in the aforementioned US-A-3730828 or JP-A-7002119. The viscosity of the resin used for the impregnation can be influenced, inter alia, by varying the nature and amount of the solvent. Uncured aminoplast resin such as melamine formaldehyde resin is, for example, dissolved in water and preferably has a viscosity of 1-1000 Pa · s. Preferably, solvents are used in which the polymeric carrier does not dissolve or swell. The temperature during impregnation is typically between 15-600C and is often room temperature for practical reasons. Higher temperatures are less practical because the resin could then fully or partially cure during impregnation. The pressure during impregnation is not critical and, for practical reasons, is usually atmospheric for 1011 4 6.9 - 12.

The carriers impregnated in this way can optionally be dried until a certain residual volatility is achieved. For melamine-5 formaldehyde (MF) and PF resins, this residual volatility is the mass loss of the prepreg at 160 ° C for 7 minutes. The residual volatility of the prepreg is usually between 2-20%. The elongation at break of the prepreg as used in the specification is defined as the elongation at break at a residual volatility of about 6 to 7% and measured at a temperature close to the processing temperature of the article.

Drying preferably takes place at a temperature of 80-160 ° C when melamine formaldehyde resin (MF resin) is used. Higher temperatures are less practical because the drying times then become too short, resulting in a process that is difficult to control. In practice, the temperature will partly be determined by the type of resin and the type of oven. The optionally dried carriers can be stacked into a multi-layered prepreg. In principle, as many sheets can be stacked on top of one another as is necessary to obtain the desired thickness and / or strength, for instance with self-supporting 2D and 3D molded parts such as lamp shades and (corrugated) sheets for interior and exterior use. For laminate application to a substrate, the number of sheet carriers is generally 100 or less, especially 10 or less, and preferably 5 or less.

The prepreg may optionally also comprise layers of a .1011468-13 non-porous polymer in addition to the porous polymer supports provided that these polymers also have an elongation to break greater than or equal to that of the prepreg.

The prepregs can be processed into a shaped final product by first deforming the prepregs and then curing the formed intermediate or by combining the deformation and curing in one step. Curing of the resin can for instance be effected by heating the prepreg, whether or not under elevated pressure, to a temperature at which the resin cures. An example of this is the curing of an MF resin. When the resin contains polymerizable groups that can react by a radical mechanism, such as, for example, an unsaturated resin, the resin can be cured by treating the prepreg with an electron beam, or irradiating the prepreg with ultraviolet or ionizing radiation. When a prepreg contains a resin which cures via a radical mechanism, it may be advantageous to add a radical initiator. The radical initiator will completely or partially disintegrate into radicals which can initiate the polymerization reaction. Well-known radical initiators are, for example, peroxides from the 2 Trigonox® series (from AKZO-NOBEL). To accelerate the initiation of the polymerization, an accelerator can be added to the resin. Well-known accelerators are, for example, cobalt complexes. The polymerization of resin which cures by a cationic mechanism and which resin is impregnated in a support can be initiated by adding a cationic initiator.

The area of the final 101 1 4 R r.

The article can be manufactured at will using techniques known to those skilled in the art. For example, a high-gloss surface can be obtained by using, for example, a gloss plate in the press, a gloss membrane or a glossy (polished) mold. Relief can be applied to and in the surface by, for example, using an etched or engraved plate in the pressing pass, using an embossed membrane or a press mold or embossed mold. Patterns can also be applied in this way. Foils between press plate or membrane and the molded part can for instance also be used. These foils can again be smooth, matt or provided with the desired pattern or relief.

Such films can optionally also be used as a membrane.

The deformation, optionally in combination with the curing, can for instance be carried out by means of bending, forming punches, 3D deformation such as 3D pressing, stamping, pneumatic or mechanical stretching.

The temperature during deformation will depend on the yield stress of the prepreg. The yield stress is the stress at which the material 25 begins to flow. In principle, this temperature can lie between room temperature and 200 ° C.

The shaped product thus obtained can be used as an end product or as a protective layer around an object with a core material of, for example, wood, wood-based fiber materials such as the known MDF (Medium Density 101 1468 - 15 -).

Fibreboard) and HDF (High Density Fibreboard) materials, metal, glass or plastic, for example polyethylene, polypropylene, ABS, polyester, polyamide, MF, PF and epoxy resins or composite objects.

The invention also relates to objects provided with a top layer obtained from a sheet-shaped prepreg which is bent along two or more intersecting axes (3D objects).

Examples of 3D end products of the shaped product are trays, dishes, crockery, lampshades, (corrugated) plates, doors, kitchen tops, furniture, wall panels. Examples of end products where the shaped product is used as a protective layer for a wooden or wood-based core are worktops with 3D structure and / or, for example, an acute angle, (kitchen) cabinets, panels with 3D structure, for example, based on milled MDF sheet, frames, laminate floors with a 3D structure (for example with raised edges), skirting 20 etc. Examples of objects in which the shaped product serves as a protective layer for a plastic core are bumpers, petrol tanks, helmets, garden furniture, chairs, counter tops or body parts. of cars.

In particular, the invention relates to sheet-shaped prepregs which provide objects with a 3D structure based on milled MDF or HDF board with a top layer. It is hereby possible to manufacture these laminated MDF or HDF boards in one process step, for example in an in-mold lamination process.

101 1468 - 16 -

The sheet-shaped articles according to the invention are also useful in flat applications (2D applications), such as laminate floors, interior of doors, wall panels, table tops, etc.

5 and in postforming applications.

Surprisingly, it has been found that when a cellulose diacetate, preferably a cellulose diacetate with a degree of substitution between 2 and 3, is used as the meltable polymer, the processing thereof into laminate, including, for example, printability, impregnability, processability and pressability, is better than with the current commercial decor paper. . Moreover, the surface properties after pressing to LPL (Low Pressure 15 Laminate) or HPL (High Pressure Laminate), such as the water absorption, dimensional stability and the possibilities for applying patterns and / or embossing, will be better than those of the known commercial decor paper. .

The top layer can be glued to the core material. Alternatively, the molded article may be applied to the core while the resin is not yet fully cured. The resin then serves as an adhesive when it is subsequently cured.

The invention will be further illustrated by the following non-limiting examples.

101 U68 - 17 -

Example I Preparation of resin

In a reactor, 100 parts of melamine, 48 parts of water and 131 parts of formalin (30% by weight of formaldehyde in water, which had been adjusted to pH 9.3 with 50% by weight of NaOH) were added. The F / M ratio of the resin was 1.65 (F / M ratio is the formaldehyde-melamine mol ratio). The melamine-formaldehyde condensation reaction was conducted at 95 ° C and this temperature was maintained until the water dilutability of the resin at 20 ° C was 1.5 g resin per g water. The water dilutability is the amount (g) of water that can be added to a resin solution (g) at 20 ° C before the solution becomes cloudy. The resin was brought to pH 7.5 at 20 ° C with a 50 wt% p-toluenesulfonic acid (catalyst) solution to make the solution suitable for further processing.

20

Preparation of sheet-shaped product

The carrier used was a so-called wet laid non-woven based on 90% by weight cellulose acetate fibers (with a degree of substitution of 2.45) and 10% by weight kraft pulp with homogeneously distributed 10% by weight diethyl phthalate (DEP) in this cellulose acetate / kraft paper pulp combination. Such a wet laid nonwoven is made by passing a paper pulp of kraft paper fibers with the cellulose acetate (CD) fibers dispersed therein over a filter to form a filter cake which is converted into a 1011468-18 sheet carrier via drying. The CD fibers were made by pouring a solution of CD into acetone in stirred ethanol. The morphology of the CD fibers is comparable to that of the paper fibers. After filtering (causing skin formation) of the aqueous CD / kraft paper pulp, the filter cake is dried. The weight of the dried sheet-shaped support is about 160 g / m2.

A sheet-like support measuring 20 by 20 cm was impregnated at room temperature with the above resin solution to which 0.5 wt.% PAT® TD80 (from Würtz) for wetting and 0.2 wt.% PAT® 523 / W (from Würtz) for release. was added. After about one minute, the resin impregnated sheet was taken out of the impregnation setup and the excess resin was removed using a wringer. The sheet was dried in a ventilation oven at 100 ° C for 8 minutes. See table 1.

20 Characterization of the prepreg

Resin Content: The resin content of the prepreg was determined by weighing the prepreg and the polymeric support and was 138%. The resin content is defined as: 25 (g (prepreg) -g (carrier)) / g (carrier) g (prepreg) and g (carrier) are the weights of the prepreg and of the polymeric carrier, respectively.

30 101 1468 - 19 -

Residual volatility: The residual volatility was determined by measuring the weight loss after further drying and curing the prepreg for 7 minutes in an oven at 160 ° C and was 6.0% by weight. The residual volatility is defined as (g (before) -g (na)) / g (before) g (before) and g (na) are the prepreg weights before 10 and after treatment at 160 ° C, respectively. See table 1.

Elongation at break and tensile strength: The elongation at break and tensile strength of the prepreg were measured on 15 test pieces (size 50.0 by 4.0 by 0.43 mm) using a Standard Zwick tensile testing machine at 140 ° C and 160 ° C according to ISO 527-2, 5A (1993). The deformation speed was 100 mm / min. For the results see table 2. 1 2 3 4 5 6 7 8 9 10 11 1011468 2D pressing on a flat surface: 2

1 sheet of the CD / kraft paper with 10 wt% DEP

3 based prepreg measuring 20 by 20 cm was pressed on 4 a flat Medium Density Fiberboard (MDF) plate to 5 a laminate according to the following low pressure laminate 6 pressing method: The MDF plate with the prepreg 7 on top was pressed (of the type Fontijne TP400) 8 after which the press was closed and brought to a pressure of 2 MPa 9. Only the top mold half - this was provided with a gloss plate - was heated and the 11 temperature was 140 ° C. These conditions were maintained for 3 minutes and then the press was opened and the laminate taken out. For press conditions see table 1. After cooling, the laminate could be characterized.

Characterization of the 2D laminate - First, the laminate was visually assessed, also using a light microscope.

The laminate looked good. On a micro scale, the structure was quite fine and resembled paper.

10 - Furthermore, it was subjected to some standard tests, in particular the staining and the Kiton test. These are known tests in the world of MF resin laminates to check that the laminate surface is closed and that the resin is sufficiently cured.

15 Below is a brief description of the results.

- The staining test used here is derived from EN 438-2 and is based on staining the laminate surface with a neutral solution of an intensive dye in an organic solvent (ethanol, methanol and a little surfactant). This solution has a highly wetting and tinting effect.

The result of the test is expressed in a numbering from 1 to 5, where 1 means: very good (no discoloration) and 5 means: very bad (very strong discoloration).

The above laminate scored 1 l.

- The Ketone test is based on staining with a sulfuric acid aqueous solution of an intensive dye. This test is also derived from EN 438-2.

101 1468 - 21 -

The result of this test is expressed in the same numerical valuation. Also in this test the laminate was rated as very good: 1. For the results of staining and Kiton test see table 3.

5

Example II

The same procedure as in example 1 was repeated, but as a porous film, a wet laid non-woven based on e.g. 80 wt% CD and 20 wt% 10 kraft paper pulp with homogeneously distributed 10 wt% DEP as a plasticizer. The weight was approximately 160 g / m2.

Table 1 lists the resin content, residual volatility content, and prepreg press conditions on MDF. Table 2 shows the elongation at break of the prepreg at the stated test temperature.

Table 3 shows the characterization of the laminate.

Example III

The same procedure as in Example 1 was repeated with a wet laid non woven. It is a blend of 35% by weight cellulose acetate fibers and 65% by weight wood pulp without plasticizer. The weight was about 100 g / m2. This nonwoven is encoded as Example 3. See Tables 1, 2 and 3 for further conditions and results.

Example IV

The same procedure as in Example 1 was repeated with a wet laid nonwoven being a blend of 50 wt.% Cellulose acetate fiber and 50 wt.% Of wood pulp without plasticizer. The weight was about 100 g / m2. The code for this is Example 4. See Tables 1, 2 and 3 for further conditions and results.

5 Example V

The same procedure as in Example 1 was repeated with a wet laid non woven. It concerns a blend of 80% by weight cellulose acetate fibers and 20% by weight wood pulp without plasticizer; code example 5. The weight was approx. 100 g / m2. See Tables 1, 2 and 3 for further conditions and results.

Example VI

The same procedure as in Example 1 was repeated, but now a wet laid non woven was used, being a blend of 80 wt.% Cellulose acetate and 20 wt.% Wood pulp. This nonwoven did not contain a plasticizer and is encoded as Example 6. The weight was about 120 g / m2. See Tables 1, 2 and 3 for further conditions and results.

Example VII

The same procedure as in Example 1 was repeated, but now a dry laid non woven was used, being a calendered carded mat based on a blend of 40% by weight cellulose acetate and 60% by weight rayon. No plasticizer has been added. The weight was about 120 g / m2. This non woven is encoded as Example 7. See Tables 1, 2 and 3 for further conditions and results.

1011468 - 23 -

Example VIII

The same procedure as in Example 1 was repeated, but now a non woven from Kimberley & Clark Corporation was used. It concerns a strong cellulose-filled polypropylene (70% by weight cellulose / 30% by weight PP) of approximately 95 g / m2. This non woven has the brand name "WORKHORSE". See Tables 1, 2 and 3 for further conditions and results.

10 Comparative experiment A

The same procedure as in Example 1 was used, but now with a decor paper (80 gr / m2) impregnated with MF resin. The elongation at break was only 0.8%. See Tables 1, 2 and 3 for further conditions and results.

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Claims (14)

Sheet-like prepreg containing one or more layers of a sheet-like porous support, which sheet-like porous support is impregnated with an as yet uncured resin, characterized in that the support contains a fusible polymer which is mixed with cellulose or regenerated cellulose or mixtures or combinations thereof. Sheet-shaped prepreg according to claim 1, characterized in that a cellulose acetate is used as the meltable polymer. 3. Sheet-shaped prepreg according to claim 2, characterized in that the cellulose acetate used has a degree of substitution between 0.01 and 3. Sheet-shaped prepreg according to claim 3, characterized in that the cellulose acetate used has a degree of substitution between 2 and 3. 5. Sheet-shaped prepreg according to claims 1-4, characterized in that kraft paper pulp is used as cellulose. Sheet-shaped prepreg according to any one of claims 1 to 5, characterized in that the elongation at break of the impregnated sheet-shaped support and of the prepreg is greater than 2%. Sheet-shaped prepreg according to claims 1-6, characterized in that the resin is an aminoplast resin. Sheet-shaped prepreg according to claim 7, characterized in that the aminoplast resin is melamine formaldehyde resin. Sheet-shaped prepreg according to claims 1-8, applied in self-supporting molded parts. 101 14; "-31 - A sheet-like prepreg according to claims 1-8 used in sheet-like articles which can be deformed along two or more intersecting axes. 11. Object provided with a top layer obtained from a sheet-shaped prepreg according to claims 1-8 which is deformed along two or more intersecting axes. Sheet-shaped prepreg according to claims 1-8 which provides articles with 3D structures based on milled MDF or HDF sheet with a top layer. Sheet-shaped prepreg according to claims 1-8 which provides objects with 2D structures with a laminate top layer. 14. Sheet-shaped prepregs and articles as follows from the description and examples. 101 14 5 'COOPERATION TREATY (PCT) REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE IDENTIFICATION OF THE NATIONAL APPLICATION Reference of the applicant or of the authorized representative 9898 NL Dutch application no. Date of application 1011468 5 March 1999 Priority date invoked Applicant's (Name) DSM NV for an international type study Awarded by the International Research Authority (ISA) to the request for an international type study. SN 32681 EN I. SUBJECT CLASSIFICATION (where different classifications apply, indicate all rating symbols) According to International Classification (IPC) Int.Cl.6: C 08 J 5/24 II. FIELDS OF TECHNIQUE EXAMINED Minimum documentation examined _Classification system__Clatsification symbols Int.Cl.6: C 08 J, D 04 M, D 06 M, D 21 H Documentation examined other than the minimum documentation for rover such documents in the areas examined are 1 □ NONE EXAMINATION FOR CERTAIN CONCLUSIONS (comments on supplementary sheet) IV. LACK OF UNIT OF INVENTION (remarks on supplement sheet Form PCT / ISA / LOUT) 07.1979