NL1011467C2 - 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 (I) comprises at least one layer of porous carrier sheet (1) impregnated with an uncured resin (2). (1) is formed on the basis of completely or partly regenerated cellulose.

Description

- 1 - VELVQRMTC? PREPREG CONTAINING SHEET CARRIERS 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, 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 resin of melamine-formaldehyde. 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-shaped product thus obtained is almost complete at the reaction temperature used (completely cured). The sheet-like articles described in the aforementioned patent 25 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 slightly along one axis (the so-called 2D-deformation whereby 2D molded parts are obtained), without the sheet-shaped article breaking or tearing.

101 14 6 7 - 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 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 based on wholly or partly regenerated cellulose. Regenerated cellulose means treated cellulose. This treatment means that cellulose is converted into a soluble cellulose derivative (usually the xantagonate), after which this cellulose derivative can be converted, for example via a spinning process, into fibers which may or may not be further reduced. Then, with the aid of an acid, this cellulose derivative is converted into regenerated cellulose. A carrier 25 is then produced from this regenerated cellulose, which is impregnated with a resin mixture, after which one or more carriers are stacked into a prepreg after drying.

Instead of a sheet-shaped porous support based on fully or partially regenerated cellulose, the sheet-shaped porous support can also be manufactured on the basis of fully or partly regenerated cellulose together with wood and / or paper pulp, in particular with kraft paper pulp. The ratio between cellulose and pulp is determined by the final application and can vary within wide limits 101 1 467-3.

The elongation at break of the separate sheet carrier and of the resulting prepreg is greater than 2%, preferably greater than 5% and especially greater than 10%. The elongation at break is measured at a temperature close to the processing temperature of the support.

It has been found that starting from the prepreg 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 articles with shapes in which the prepregs are stretched locally during molding from 10% to more than 100% are now possible.

Articles where the required maximum deformation is less than 10% can also be coated better with the sheet-shaped product according to the invention than with paper-based sheet-shaped products. 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, so that the most optimal technique can always be applied for each end product.

101 1467 - 4 -

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 further possible to make sheet-shaped products which are bent to an acute angle. This is not possible on the basis of the known prepregs on the basis of a paper carrier.

A sheet-shaped 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 support can be mixed 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 part consists of resin.

The porous support based on fully or partially regenerated cellulose will preferably be a woven or a non-woven, a sheet-like open foam or a microporous membrane. Fully or partially regenerated celluloses are commercially available, inter alia, under the generic names viscose and rayon or the brand name Lyocell® (a product of Acordis) etc. These rayons and viscoses are prepared by cellulose, which is the main component of, for example, wood or paper pulp, to be modified 101 14 6 7 - 5 - for example by turning it into a xantagonate. These cellulose xantagonates, in contrast to cellulose itself, are soluble and spinnable, so that threads can be obtained. These threads are then fully or partially regenerated in an acid medium, resulting in threads of cellulose. Threads of Lyocell® are obtained by spinning from a cellulose solution in N-methylmorpholine N-oxide (NMNO). By extracting NMNO from the resulting wires via extraction with water, wires of regenerated cellulose are formed.

All these threads can then be converted into fibers, for example by reducing the threads, which fibers can be used for the production of, for example, wovens or non-wovens. 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. Polymer foams have interconnected cavities, the cavities preferably having 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.

The sheet-like porous support may have both polar and non-polar properties. Preferably, the polar properties should predominate. By using suitable wetting agents, the desired degree of impregnation of the sheet 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 (Nonidet® P40 is a brand name of Sigma Chemie) and Aminol® N (Aminol® is a brand name of Chem-Y).

101 u 6? - 6 -

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 5 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, such as, 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 curable resins can contain monomers containing polymerizable 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 that cure via an addition or 101 1 467 - 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 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. 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-25 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. It is possible that these resins are prepared and / or cured in 101146? - presence of a catalyst and / or initiator specific for each resin system, all this as known to the person skilled in the art.

Practically well applicable mechanical properties are achieved if 10-70 wt.% Porous support is used and 90-30 wt.% Resin. The resin can contain the known fillers, pigments and / or dyes, as known, for example, from the paper industry. Examples are lime, titanium dioxide, iron oxide, glass, carbon, silica and / or 10 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 20 used for the impregnation can be influenced, inter alia, by varying the nature and amount of the solvent. For example, not yet cured aminoplast resin such as melamine formaldehyde resin is dissolved in water and preferably has a viscosity of 1-1000 Pa.s. Preferably, solvents are used in which the 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 then fully or 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 reached. For melamine-formaldehyde (MF) and phenol-formaldehyde (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 2-5 and 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% by weight 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 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 15 oven. The optionally dried carriers can be stacked into a multi-layered prepreg. In principle, as many sheets can be stacked on top of each other as is necessary to obtain the desired thickness or strength, for example with self-supporting 2D and 3D molded parts such as lampshades and 20 (corrugated) plates for indoor and outdoor use. For laminate applications, the number of sheet carriers is generally 100 or less, especially 10 or less, and preferably 5 or less.

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

The prepregs can be processed into a molded end 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 effected, 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 unsaturation-containing 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 Trigonox® series (from AKZO-nobel). To accelerate the initiation of the polymerization, an accelerator can be added to the resin. 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 using a press mold or embossing die. 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 starts to flow. In principle, this temperature can be between room temperature and 200 ° C.

The shaped product thus obtained can be used as a final product or as a protective layer around an object with a core material of, for example, wood; wood-based materials such as the well-known MDF (Medium Density Fiberboard) and HDF (High Density Fiberboard); metal; glass; plastic, for example polyethylene, polypropylene, ABS, polyester, polyamide and MF, PF and epoxy resins or composite articles.

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 molded product are trays, dishes, crockery, lampshades, (corrugated) plates, doors, kitchen tops, furniture and wall panels. Examples of 3D end products where the 101 1467 - 12 - shaped cured product is used as a protective layer for a wooden or wood-based core are worktops with a 3D structure and / or, for example, an acute angle, (kitchen) cabinets, frames, panels with 3D-5 structure, for example, based on milled MDF or HDF board, laminate floors with a 3D structure (for example, raised edges), baseboards, etc. Examples of 3D objects in which the shaped product serves as a protective layer for a plastic core are bumpers, 10 petrol tanks, outdoor furniture, chairs, helmets, counter tops or car body parts.

In particular, the invention relates to sheet-shaped prepregs that provide objects with 3D structures based on milled MDF or HDF board 15 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.

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

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

Preparation of resin 35 In a reactor, 100 parts of melamine, 48 parts of water and 1011467 - 13 - 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 condensation reaction 5 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% p-10 toluenesulfonic acid solution to make the solution suitable for further processing.

Preparation of sheet-shaped product

A sheet-like support of 100 wt.% Rayon, 120 g / m2 (from the 15 Lenzing AG) measuring 20 by 20 cm was impregnated at room temperature with the above-mentioned resin solution to which 0.5 wt.% PAT © TD80 (from the company Würtz) for wetting and 0.2 wt% PAT® 523 / w (from Würtz) before release was added. After one minute, the resin-impregnated 20 sheets were 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 16 minutes. See table 1. 1 1011467

Characterization of the prepreg

Resin Content: The resin content of the prepreg was determined by weighing the prepreg and the polymeric support and was 415%. See Table 1. The resin content is defined as: 30 (g (prepreg) -g (carrier) / g (carrier) g (prepreg) and g (carrier) are the weights of the prepreg and of the rayon carrier, respectively.

- 14 -

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 5 was 6.8%. See Table 1. The residual volatility is defined as: (g (before) -g (after)) / g (before) 10 g (before) and g (after) are the weights of the prepreg before and after treatment at 160 ° C, respectively.

Elongation at break and tensile strength: The elongation at break and tensile strength are measured on test specimens (size 4 by 50 by 0.7 mm) 15 using e.g. a Standard Zwick Tensile Bench at 140 ° C and 160 ° C according to ISO 527-2, 5A (1993) and amounted to 61 resp. 73%. The deformation speed was 100 mm / min. See table 2.

2D pressing on a flat surface: 20 1 sheet of a rayon-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 was introduced into the press (Fontijne TP400), after which the press was closed and brought to a pressure of 20 bar. Only the top mold half, which is provided with a gloss plate, was heated and the temperature was 140 ° C. These conditions are maintained for 3 minutes and then the press is opened and the laminate taken out. See table 1. After cooling, the laminate could be characterized.

101 1467 - 15 -

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

On a micro scale, the structure was very fine and resembled 5 paper. The laminate surface contained no air entrapment and looked tightly closed.

- 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 whether the laminate surface is closed and whether the resin has sufficiently cured. 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 l 20 means: very good (no discoloration) and 5 means: very bad (very strong discoloration). The above laminate scored a 1.

- The Ketone test is based on staining with a sulfuric aqueous solution of an intensive dye. This 25 test is also derived from EN 438-2. 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 results of Staining and Kiton test see Table 3.1 101 1467

Example II

The same procedure as in Example 1 was repeated, however, as the porous film was now used: Matt Lyocell®, 105 g / m2, 1.7 d'tex 38 mm (from Acordis).

Table 1 shows 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.

5

Example III

The same procedure as in Example 1 was repeated, but now Matt Lyocell®, 60 g / m2, 1.7 d'tex 8 mm (Acordis) was used. See Tables 1, 2 and 3 for further conditions and results.

Example IV

The same procedure as in Example 1 was repeated, but now TAT® 2121 (Freudenberg) was used.

15 This is a non-woven based on rayon. See Tables 1, 2 and 3 for further conditions and results.

Example V

The same procedure as in Example 1 was repeated using T1710® (45g / m2) from Freudenberg. This is a non-woven based on rayon. See Tables 1, 2 and 3 for further conditions and results. 1 1011467

Comparative experiment A

The same procedure as in Example 1 was used, but instead of 100% rayon, 120 g / m2 (Lenzing AG), a decor paper (80 gr / m2) was used. See Tables 1, 2 and 3 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 a resin which has not yet been cured, characterized in that the support is a sheet-shaped porous support based on fully or partly regenerated cellulose. 2. Sheet-shaped prepreg according to claim 1, characterized in that the sheet-shaped porous support is based on wholly or partly regenerated cellulose together with wood and / or paper pulp. Sheet-shaped prepreg according to claim 2, characterized in that kraft paper pulp is used as wood and / or paper pulp. Sheet-shaped prepreg according to any one of claims 1-3, characterized in that the porous support is a sheet-shaped woven or non-woven, a sheet-shaped open foam or a microporous membrane. Sheet-shaped prepreg according to any one of claims 1 to 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 is meiamine formaldehyde resin. Sheet-shaped prepreg according to claims 1-7, applied in self-supporting molded parts. Sheet-shaped prepreg according to claims 1-7, used in sheet-shaped products which can be deformed along two or more intersecting axes. 10. Object 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. 1011467 - 22 - 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 objects 5 with 2D structures with a laminate top layer. 13. Sheet-shaped prepregs and articles as follows from the description and examples. 1011467 COOPERATION TREATY (PCT) REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE IDENTIFICATION OF THE NATIONAL APPLICATION Characteristic of the applicant ol of the authorized representative 9899 NL The Netherlands Application no. of international type O ear the Initiation for International Research (ISA) granted to the request for an international type investigation. SN 32680 EN I. CLASSIFICATION OF THE EDUCATION RP (in case of different classifications, indicate all classification symbols) According to the International Cleoification (IRC) Int.Cl.6: C 08 J 5/24 II. FIELDS OF TECHNIQUE EXAMINED Minimum Documentation Clause Claims System Clause Symbol Int. 1 NO RESEARCH POSSIBLE FOR CERTAIN CONCLUSIONS (comments on supplement sheet) IV- 1 1 LACK OF UNIT OF INVENTION (comments on supplement sheet) ^ form PCT / ISa / 30Uj1 07.1979