NL1011466C2 - Sheet prepreg useful for covering flexible sheet products and molded articles comprises at least one layer of carrier sheet impregnated with uncured resin - Google Patents

Abstract

A sheet prepreg comprises one or more layers of a carrier sheet which has been impregnated with an uncured resin, the carrier comprising a porous carrier sheet containing a fibrous cellulose ester, preferably several esters and in particular cellulose acetate.

Description

- 1 - SHEET-PREPREG CONTAINING SHEET CARRIERS AND NON-CURED RESIN 5

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 carriers stacked on top of each other and impregnated with the reaction product of formaldehyde and melamine are known, for example, from US-A-3730828. According to this patent, paper 15 is first impregnated with a melamine-formaldehyde resin. A prepreg is then made by drying a few layers of this impregnated paper and stacking 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 obtain a sheet-like product. The reaction between formaldehyde and melamine in the sheet-like product thus obtained is completely (completely cured) at the temperature used. The sheet-like articles described in the aforementioned patent appear to have good postforming properties.

By postforming 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 along one axis (the so-called 2D deformation whereby 2D molded parts are obtained) without the sheet-shaped article breaking and / or tearing.

.e . ·. f; - 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 a prepreg with which more complex shapes can be obtained and / or covered.

This object is achieved with a prepreg consisting of one or more layers of a sheet-shaped support, which support is impregnated with an as yet uncured resin, the support being a sheet-shaped porous support containing a fibrous cellulose acetate. Preferably, fibrous cellulose acetate is used, 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 and cellulose triacetate, as well as mixtures or combinations of these acetates. Preferably, the degree of substitution is between 2 and 3.

In particular, the carrier used is fibrous cellulose diacetate in which the cellulose diacetate is in the form of fiber bundles, the so-called CD-tow, and in which the individual fibers have a diameter of less than 100 µ, preferably less than 50 µ. The diameter of the individual fibers is greater than 1 μ.

It is also possible to use fibrous cellulose acetate in the form of yarns. These yarns can be prepared on a CD-tow basis. Bundles made up of yarns can also be used.

The carrier based on a fibrous cellulose acetate will preferably also contain a plasticizer. 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. As plasticizer, any plasticizers known for cellulose acetates can be used, such as 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.

The elongation at break of the prepreg and of the individual impregnated support is greater than 2%, preferably greater than 5%, and especially greater than 10%. The elongation at break is 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 starting from the prepreg 30 according to the invention, sheet-shaped products can be made in the most diverse shapes without cracks being formed in the sheet-shaped product during deformation.

Sheet-shaped moldings - 4 - with the prepregs locally stretched from 10% to more than 400% during molding are now possible. Articles where the required maximum deformation is less than 10% can also be coated better with the sheet-shaped article 5 according to the invention than with paper-based sheet-shaped 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, in which two steps are required starting from the prepreg to arrive at a formed end product.

An additional advantage is that the prepreg can be processed with a variety of techniques, 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 objects can be coated, making it possible to obtain an identical decor on both objects, for instance the decor of a 3D kitchen cupboard 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.

* ij 5 Π ^ - 5 -

A sheet-like porous support is understood to mean any support which has a high degree of porosity. The porosity of the support is essential to obtain the advantageous properties of the prepreg as described above. Due to the high porosity, the sheet-shaped carrier can, as it were, be filled almost homogeneously with the resin. Preferably, the porosity is obtained in the form of microscopically small interconnected voids and preferably slightly larger voids and holes are present. Larger 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 support can be, for example, a woven or non-woven sheet support, a sheet-shaped open foam support or a microporous membrane. Preferably, the diameter of the fibers of the nonwoven 20 is 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 non-woven fabrics has few larger meshes and many microscopically small interconnecting cavities.

The sheet-like porous support may have both polar and non-polar properties. By using suitable wetting agents, the desired degree of impregnation of the support by the resin 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 - 6 - (Nonidet® P40 is a brand name of Sigma Chemie) and 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 can be cured by an ionic, radical, oxidation, addition or condensation mechanism or by 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 via a condensation or addition reaction.

Cationic or radically curable resins can cure by a homopolymerization or a copolymerization reaction. Radically curable resins can contain unsaturated monomers and / or groups which include (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 can contain monomers 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 - 7 - condensation mechanism are, for example, aminoplast resins, phenol formaldehyde resins (PF resins) and / or two-component resins consisting of hydroxyl-functional polymers or oligomers and 5-isocyanate-functional oligomers or polymers and / or alkylated melamine resins.

An aminoplast resin is preferably 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. Also 20 modifiers can 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 and / or combinations of resins which can be cured according to different 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.

- 8 -

Practically useful mechanical properties are achieved if 10-70 wt.% Porous support is used and 90-30 wt.% Resin. The resin can contain the known fillers and / or dyes such as lime, clay, glass, carbon, silica, titanium dioxide or metal particles. However, it has been found that the best results are achieved in the absence of fillers or in any case 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. The viscosity of the resin used for the impregnation can be influenced, for example, 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 15-60 ° C and is often room temperature for practical reasons. Higher temperatures are less practical because the resin could partially cure during impregnation. The pressure during impregnation is not critical and, for practical reasons, is usually atmospheric.

The carriers thus impregnated can optionally be dried until a certain residual volatility is obtained. For melamine-formaldehyde (MF) resins 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% and measured at a temperature close to the processing temperature of the article. Drying takes place when using MF resin, preferably at a temperature of 100-160 dC. Higher temperatures are less practical because the drying times then become too short, resulting in a less controllable process. The optionally dried carrier 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, for example with 20 self-supporting 2D and 3D molded parts such as lampshades or (corrugated) sheets for indoor and outdoor use. For laminate application, the number of sheet carriers is generally 100 or less, preferably 10 or less, and especially 5 or less.

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

The prepreg can be processed into a finished finished product by first deforming the prepreg and then curing the formed intermediate or by combining the deformation and curing in one step. Curing of the resin can be accomplished, for example, 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 15 will completely or partially disintegrate into radicals which can initiate the polymerization reaction. Well-known radical initiators are, for example, peroxides from the 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 surface of the final 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 shiny (polished) mold. Embossing can be applied to and into the surface by, for example, using an etched or engraved plate in the pressing pass, using an embossed membrane or - 11 - an embossing mold or press 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 the deformation will depend on the yield stress of the prepreg. The yield stress is the stress at which the material starts to flow. In principle, this temperature can be between room temperature and 200 ° C.

The shaped article 20 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 or wood-based material such as the known MDF (Medium Density Fibreboard) and HDF (High Density Fibreboard); metal; glass; plastic, for example polyethylene, polypropylene, ABS, polyamide, polyester and MF, PF and epoxy resins or combinations thereof.

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

Examples of 3D end products of the f 0 i j.

- 12 - formed product are trays, dishes, crockery, lampshades, (corrugated) plates, doors, kitchen tops, furniture and wall panels. Examples of end products where the shaped product is used as a protective layer for a wooden or wood-based core are counter tops with 3D structure and / or, for example, an acute angle, (kitchen) cabinets, panels with 3D structure, for example, based on milled MDF or HDF board, frames, laminate floors 10 with 3D structure (eg with raised edges), skirting boards, 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, furniture, counter tops or body 15 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 sheet with a top layer. It is hereby possible to manufacture these 20 laminated MDF or HDF boards in one process step, for example in an in-mold lamination process.

The sheet-shaped products according to the invention are also useful in flat applications (2D applications), for example laminate floors, inner sides of doors, wall panels. table tops etc. 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 instance printability, - impregnability, processability and pressability, proceeds at least as well. as with the current commercial decor paper. Moreover, the surface properties after pressing to LPL (Low 5 Pressure 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. .

10 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.

Example I

Resin preparation

In a reactor, 100 parts of melamine, 48 parts of water and 131 parts of formalin (30 wt.% Formaldehyde in 25 water which had been adjusted to pH 9.3 with 50 wt.% NaOH) were added. The F / M ratio of the resin was 1.65 (F / M ratio is the formaldehyde-melamine molar ratio). The condensation reaction was carried out at 95 ° C 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% paratoluene sulfonic acid solution (catalyst) to make the solution suitable for further processing.

5 Preparation of sheet-shaped product

The carrier used was a wet laid non-woven based on 100 wt.% Cellulose diacetate (CD) in the form of fibers with 10 wt.% Diethyl phthalate (DEP) as plasticizer homogeneously distributed therein. The CD fibers 10 are made by pouring a solution of CD into acetone in stirred ethanol. A wet laid non-woven is made by passing a dispersion of CD fibers in water over a filter to create a filter cake that is converted into a carrier through drying. The morphology of the obtained CD fibers is fine and comparable to that of paper fibers in paper pulp. The weight of the dried film in this example was 80 g / m2.

For the 2D pressing a sheet measuring 20 by 20 cm.

20 used. For the 3D pressing, a circular sheet with a diameter of 21 cm was used.

The sheets were 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 had been added. After 30 seconds, the resin impregnated sheet was taken out of the impregnation setup and the excess resin was removed with a wringer. The sheet was dried in a ventilation oven at 100 ° C for 8 minutes. See Tables 1a and 1b.

- 15 -

Characterization of the prepreg

Resin Content: The resin content of the prepreg was determined by weighing the prepreg and the support and was 138%. The resin content is defined as: 5 (g (prepreg) -g (carrier)) / g (carrier) g (prepreg) and g (carrier) are the weights of the prepreg and of the carrier, respectively. See Tables 10 la and lb.

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%. The residual volatility is defined as (g (before) -g (na)) / g (before) 20 g (before) and g (after) are the prepreg weights before and after treatment at 160 ° C, respectively. See Tables 1a and 1b.

Elongation at break and tensile strength: The elongation at break and tensile strength were measured on test specimens (size 50.0 by 4.0 by 0.52mm) using a Standard Zwick pull bench at 140 and 160 ° C according to ISO 527-2, 5A (1993). The deformation speed was 100 mm / min. For the results see table 2.

30 - 2D. pressing on a flat surface:

1 sheet of the non-woven on CD with 10% by weight DEP

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

- 3D pressing: 15 To be able to assess the final deformation of the prepreg, a square motif was applied to it with a pencil.

A circular sheet of the CD nonwoven with 10 wt% DEP based prepreg with a diameter of 21 cm 20 was pressed on so-called REMEL (REinforced MELamine) Sheet Molding Compounds (SMC). These are thin (approx. 3 mm thick) glass mats, filled with partially cured MF resin.

First of all, a prepreg was clamped above the bottom of a mold that was in the shape of a round tray. A number of stacked and preheated REMEL SMCs were placed on the clamped prepreg. The input of SMCs is approx. 60% compared to the surface of the mold. The final molded part 30 was created by means of blotting presses, whereby the molding sheets flow out and fill the mold to the final shaped part. The prepreg was hereby stretched over the REMEL core as a skin. During this process, deformation, curing and bonding of the prepreg with the substrate took place in one step.

Pressing was carried out at 140 and 160eC with a pressure of 10 MPa 5 (High Pressure Laminate = HPL) with the following pressing cycle: inserting, closing and pressurizing, venting (after 25 seconds), closing again and pressurizing, this pressure some time (at 140 ° C: 315 seconds, at 160 ° C: 155 seconds), after which the press 10 could be opened and the molded part removed. After cooling, the laminate could be characterized.

Characterization of the 2D laminate (see table 3a) 15 - The laminate was visually assessed and also viewed with a light microscope.

The laminate looked good and was homogeneous on a macro scale. The laminate surface was smooth and closed.

20 - Furthermore, the laminate 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.

25 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 (strong discoloration).

5 The above laminate scored a 1, very well.

- The Ketone test is based on staining with a sulfuric aqueous solution of an intensive dye. This test is also derived from EN 438-2. The result of this test is expressed in the same 10-digit valuation.

Also in this test, the laminate was rated as very good: 1.

Characterization of the 3D laminate (see table 3b) 15 - Compression at 140 ° C:

The prepreg was provided uniformly around the REMEL core. The surface was fairly smooth and closed in appearance. Result Staining test: 4 Result Kiton test: 4 20 - Compression at 160 ° C:

The distortion of the prepreg is good. The surface was smooth and otherwise closed.

Result Staining Test: 1 25 Result Kiton Test: 2

example II

In this example, a dry laid non-woven based on 100% cellulose diacetate tow was used. Tow is made on a large scale by spinning a solution of cellulose diacetate in acetone, after which the acetone is evaporated.

i o1 n * - - 19 -

Tow is a bulk product that is used, among other things, in cigarette filters.

Tow fibers are processed into a non-woven. After cutting the tow to about 5 cm. long pieces were carded to a felt-like mat. Several of these mats are stacked on top of each other in different directions of orientation and glued together to form a multi-layer mat, which is then calendered at elevated temperature.

This creates an extremely beautiful and very strong 10 non-woven foil. Afterwards 10% DEP was added as a plasticizer by spraying from a solvent. The weight of the foil was approximately 150 g / m2.

-2D pressing has taken place in accordance with Example 1. See Tables 1a, 2, and 3a for further data and results.

-3D pressing. The foil was impregnated with MF resin with a pH of 8.0. In one press run, the prepreg obtained after drying was pressed on a core of wood fiber-filled phenol formaldehyde resin (PF).

This is done in a 3D shaped aluminum mold. The pressed product has the shape of a plate with a hemisphere punched in it. Pressing was carried out at a pressure of 25 MPa for 15 minutes at 140 ° C. Under these conditions good curing of both the core and the laminate was obtained.

Table 1b, 2 and 3b list conditions and results.

30

Comparative experiment A

The same procedure as in example 1 - 20 - has been used, but now with a decor paper (80 g / m2). See Tables 1a, 1b, 2, 3a and 3b for further conditions and results.

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Claims (13)

1. Sheet-shaped prepreg consisting of one or more layers of a sheet-shaped support, which support is impregnated with an as yet uncured resin, characterized in that the support is a sheet-shaped porous support containing a fibrous cellulose acetate. Sheet-shaped prepreg according to claim 1, characterized in that the sheet-shaped porous support is based on cellulose acetate with a degree of substitution between 0.01 and 3. Sheet-shaped prepreg according to claims 1-2, characterized in that the fibrous cellulose acetate is in the form of fiber bundles. 4. Sheet-shaped prepreg according to any one of claims 1-3, characterized in that the porous support is a sheet-like woven or non-woven, a sheet-shaped open foam or a microporous membrane. 5. Sheet-shaped prepreg according to any one of claims 1-4, 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 1-5, characterized in that the resin is an aminoplast resin. Sheet-shaped prepreg according to claim 6, characterized in that the aminoplast resin 30 is melamine formaldehyde resin. Sheet-shaped prepreg according to claims 1-7, applied in self-supporting molded parts. 9. Sheet-shaped prepreg according to claims 1-7 used in sheet-shaped products which can be deformed along two or more intersecting axes. - 27 - An article provided with a top layer obtained from a sheet-shaped prepreg according to claims 1-7 which is deformed along two or more intersecting axes. A sheet-shaped prepreg according to claims 1-7 which provides articles with 3D structures based on milled MDF or HDF sheet with a top layer. 12. Sheet-shaped prepreg according to claims 1-7 which provides 10 objects with 2D structures with a laminate top layer. 13. Sheet-shaped prepregs and articles as follows from the description and examples. to '46 COOPERATION TREATY (PCT) REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE IDENTIFICATION OF THE NATIONAL APPLICATION Characteristic of the applicant or of the authorized representative 9900 NL Dutch application no. Filing date 1011466 March 5, 1999 Priority date claimed Applicant (Name) DSM NV an investigation of an international type Granted by the International Research Authority (ISA) to the request for an investigation of an international type 'No. SN 33059 EN I. SUBJECT CLASSIFICATION (where different classifications apply, indicate all badger symbols) According to International Classification (IPC) Int.Cl.6: C 08 J 5/24 II. FIELDS OF TECHNIQUE EXAMINED _ Minimum documentation examined Classification system_ Clause symbols Int.Cl.6: C 08 J, D 04 M, D 06 M, D 21 H Documentation examined other than the minimum documentation to the extent that such documents are in the areas examined O0 $ enomen 4 * Itl · \] NO RESEARCH POSSIBLE FOR CERTAIN CONCLUSIONS (comments on supplementary sheet) rJV. f 1 LACK OF UNIT OF INVENTION (comments oo supplement sheet ÉOi-m PCT / rSa / IOUs) 07.1979