CA2302618A1 - Laminar prepreg - Google Patents
Laminar prepreg Download PDFInfo
- Publication number
- CA2302618A1 CA2302618A1 CA002302618A CA2302618A CA2302618A1 CA 2302618 A1 CA2302618 A1 CA 2302618A1 CA 002302618 A CA002302618 A CA 002302618A CA 2302618 A CA2302618 A CA 2302618A CA 2302618 A1 CA2302618 A1 CA 2302618A1
- Authority
- CA
- Canada
- Prior art keywords
- laminar
- prepreg
- resin
- carrier
- impregnated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 15
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 6
- 239000000969 carrier Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 239000011241 protective layer Substances 0.000 claims description 5
- 239000000080 wetting agent Substances 0.000 claims description 5
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 18
- -1 polyethylene Polymers 0.000 description 11
- 239000011162 core material Substances 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 229920001747 Cellulose diacetate Polymers 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004775 Tyvek Substances 0.000 description 3
- 229920000690 Tyvek Polymers 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
Abstract
Laminar prepreg comprising one or more layers of a laminar carrier, which carrier is impregnated with an as yet uncured resin, the carrier being a laminar porous polymer and the elongation at break of the prepreg and of the separate impregnated laminar carrier being greater than 10 %.
Description
The invention relates to a laminar prepreg comprising one or more layers of a laminar carrier, which carrier is impregnated with an as yet uncured resin.
l0 Laminar prepregs comprising a plurality of mutually stacked layers of a-cellulose impregnated with the reaction product of formaldehyde and melamine are disclosed, for example, in US-A-3730828. According to said patent publication, paper is first impregnated with a melamine-formaldehyde resin. Then a prepreg is made by precuring layers and thereafter stacking a few layers of said impregnated paper on top of one another. The resin is then cured in a press under a pressure of, for example, 6 MPa and at a temperature of approximately 150°C. The conversion of the reaction between formaldehyde and melamine in the laminar product thus obtained is complete (completely cured). The laminar products described in said patent publication appear to have good postforming properties. Postforming is understood as meaning that the laminar product can be bent at an elevated temperature which is between 160 and 180°C, it being possible to bend the laminar product along one axis without the laminar product breaking/cracking.
A disadvantage is that, starting from a prepreg according to US-A-3730828, it is not possible to WO 99/13000 PCT/NL9$/00469 obtain laminar products which can be bent into complex shapes along two (or more) mutually intersecting axes without breaking/cracking. Complex shapes may be considered to be, for example, a saddle-type pattern, a small tub, a sickle pattern or a satchel.
The object of this invention is a prepreg with which more complex shapes can be obtained.
This object is achieved in that the carrier is a laminar porous polymer and in that the elongation at break of the prepreg and of the separate impregnated carrier is greater than 10%.
It has been found that, proceeding from the prepreg according to the invention, laminar products can be made in the most diverse shapes without cracks occurring in the laminar product during the deformation.
Laminar products are now possible which have shapes in which the prepregs are locally stretched from lo% to more than 400% during the shaping. A further advantage is that the further curing of the resin and the deformation can be performed in one step. This is in contrast to the method described in the above-mentioned US-A-3730828 where, proceeding from the prepreg, two steps are necessary to arrive at a shaped final product.
An additional advantage is that the prepreg can be processed by a multiplicity of techniques, as a result of which the most optimum technique can be used for each final p=oduct.
Proceeding from the prepreg according to the invention, it is furthermore possible to make laminar products which are bent into an acute angle, for example along one axis. Proceeding from the known prepregs based . . _ 3 _ on a paper carrier, this is impossible.
JP-A-7002119 discloses a prepreg made up of a carrier of a polyamide nonwoven material and a carrier of kraft paper, which carriers are impregnated with a melamine-formaldehyde resin. An impregnated polyamide nonwoven carrier has, as a rule, an elongation at break of more than 10%. However, impregnated kraft paper has an elongation at break of less than 10%, as a result of which the elongation at break of the prepreg as a whole is less than 10%.
A laminar porous polymer carrier is understood as meaning any polymer which comprises a high degree of porosity. The porosity of the polymer carrier is essential for obtaining the advantageous properties of the prepreg as described above.
As a result of the high porosity, the laminar polymer carrier can, as it were, be mixed almost homogeneously with the resin. Preferably, the porosity is obtained in the form of microscopically small, mutually communicating cavities and there are preferably few larger cavities and holes present. Larger holes result in loss of resin during the further processing of the prepreg to its final shape. Preferably, the porosity is sufficiently high for at least 30% by volume of the final shaped part to consist of resin. The porosity is the ratio between the density of the porous polymer carrier with respect to that of the corresponding bulk polymer (no cavities).
The porous polymer carrier may, for example, be a nonwoven laminar polymer, a laminar open polymer foam or a microporous membrane. Preferably, the fibres of the nonwoven are smaller than 0.1 mm. Nonwovens having very small-diameter fibres are also referred to as open films. This class of nonwovens has, as a result of the small thread diameter, few larger meshes and many microscopically small, mutually communicating cavities.
The fibres of said nonwovens lie, as a rule, parallel to the plane of the laminar porous polymer. Polymer foams inherently have a reasonably definable and uniform size of the mutually communicating cavities. The cavities l0 preferably have a diameter of less than 1 mm. Larger cavities may occasionally be present in the foam provided more than 80% by volume of the cavities have said smaller diameters.
The porous polymer carrier may in principle be any porous polymer which meets the requirement that the impregnated carrier has an elongation at break of more than 10%. Examples of porous polymers are porous polyethylene, porous polypropylene, porous polystyrene, porous ethylene/propylene copolymers, porous EPDM, porous polyamides, for example, porous nylon 6,6, porous nylon 6, porous ethylcellulose, porous cellulose acetates, for example porous cellulose diacetate, porous SMA/SAN, porous polyesters, for example porous polyethylene terephthalate (PET), porous polybutylene terephthalate (PBT), porous polyethers. Also possible are combinations of different porous polymers or combinations of porous polymers with paper. As porous polymer carrier, the above-mentioned polymers can be used as nonwoven, open film or open polymer foam.
Examples of an open-film polyethylene are the polyethylene types which are known under the name of Solupor (Solupor is a DSM N.V. brand name). Nonwovens based on various polymers are suitable to be used as carrier. An example of a nonwoven polyethylene is Tyvek (Tyvek~ is a DuPont de Nemours brand name). An example of a nonwoven polypropylene is Lutrasil~ (Lutrasil~ is a Freudenberg brand name). An example of a nonwoven polyester is Viledori H1206. An example of a nonwoven polyamide is Viledon FS2118 (Viledon is a Freudenberg brand name). An example of an open polymer foam is Calligan open-cell foam standard 1.17 polyether (Calligari is a Calligan Europe B.V. brand name). An example of a cellulose filled nonwoven polypropylene is Workhouses (Workhouses is a Kimberly-Clark brand name).
An example of a nonwoven cellulose acetate is TAT 2121 which is a product of Freudenberg.
The polymer may have either polar or apolar properties. As a result of making use of suitable wetting agents, the desired degree of impregnation of the polymer sheet by the resin can be obtained. As a rule, all the wetting agents known to the person skilled in the art can be used. Examples of wetting agents are PAT 523W, PAT 959 (PAT is a Wiirtz brand name), Nonidet~ P40 (Nonidet~ P40 is a Sigma Chemie brand name) and Aminol~ N (Aminol~ is a Chem-Y brand name).
The resin may in principle be any known thermosetting resin. Examples are aminoplast formaldehyde resin, phenol-formaldehyde resin (PF
resin), epoxy resin or unsaturated polyester resin.
Preferably, an aminoplast-formaldehyde resin is used as resin. Urea, melamine or benzoguanamine, for example, can be used as aminoplast. Preferably, melamine is used because of its superior mechanical properties.
The resin can be prepared in a process known to the person skilled in the art by reacting aminoplast and formaldehyde in water. The ratio of, for example, formaldehyde:melamine is normally speaking between 1:1 and 6:1, preferably between 1.2:1 and 2:1. Optionally, the aminoplast can be partially replaced by, for example, phenol, but this may have adverse effects on the colour. Modifiers, such as sorbitol, s-caprolactam, l0 ethylene glycol, trioxitol, toluenesulphonamide, and benzo- and acetoguanamine can also be added.
Mechanical properties which can be used well in practice are achieved if 10-70% by weight of porous polymer and 90-30% by weight of resin are used. The resin may contain the known fillers such as lime, clay, glass, carbon, silica or metal particles. It has been found, however, that the best results are achieved in the absence of fillers or at any rate with less filler than has been usual hitherto. The filler and resin weight ratio is preferably between 0:1 and 0.5:1. These ratios relate to the cured, final laminar product.
The prepreg comprises one or more stacked sheets of the impregnated porous polymer carrier. The number of laminar carriers is, as a rule, 10 or lower, and preferably 5 or lower. The thickness of the prepreg can vary from 100 ~m to approximately 3 cm. The degree to which the resin is cured in the prepreg can be determined for melamine-formaldehyde (MF) and PF resins by determining the residual volatility. Said residual volatility is the loss in mass of the prepreg during 7 minutes at 160°C. The residual volatility of the prepreg is, as a rule, between 2 and 20%. The elongation at break of the prepreg as used in the description is defined as the elongation at break for a residual volatility of approximately 5%.
The prepreg is made under the conditions which are already known for making prepregs based on a paper carrier, as described, for example, in the above-mentioned US-A-3730828 or JP-A-7002119. The resin is preferably dissolved in water and is water-fluid , the resin preferably having a viscosity of 1-1000 Pa.s. The viscosity can be influenced by varying the amount of solvent. The solvent will vary depending on the chosen resin. Still uncured aminoplast-formaldehyde is preferably dissolved in water. Preferably solvents are used in which the polymer carrier does not dissolve or swell. The temperature during the impregnation may be between 15 and 60°C and, for practical reasons, is often room temperature. Higher temperatures are less practical because the resin partially cures during the impregnation. The pressure during the impregnation is not critical and, for practical reasons is, as a rule, atmospheric.
The carriers impregnated in this way are dried until the residual volatility is reached, as described above for the prepreg. The drying preferably takes place at a temperature of 100-160°C. Higher temperatures are less practical because the drying times then become too short, resulting in a less controllable process. The temperature will in practice also be determined by the type of oven. Preferably, the carrier is stacked after the drying.
WO 99/13000 PCT/NL98/004b9 _ _ g _ The elongation at break of the separate impregnated carrier (residual volatility = approximately 5%) and of the prepreg obtained is greater than 10% and preferably greater than 50%. The prepreg may optionally also comprise layers of a non-porous polymer in addition to the porous polymer carriers provided these polymers also have an elongation at break which is greater than or equal to that of the prepreg.
The prepreg can be processed into a shaped final product by first deforming the prepreg and then curing the shaped intermediate product at elevated temperature or by combining the deformation and the curing in one step.
The deformation, optionally in combination with the curing, can be performed by means of bending, embossing, stamping, pneumatically stretching or mechanically 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 begins to flow. Said yield stress is determined by the resin composition, resin content, polymer type and water content. In principle, said temperature may be between room temperature and 200°C. At temperatures higher than 100°C, the resin will already (partially) cure during the deformation, as a result of which the deformation and curing of the resin will take place simultaneously.
The shaped product obtained in this way can be used as final product or as protective layer around an object having a core material of, for example, wood, metal, glass or plastic, for example polyethylene, _ _ 9 polypropylene, ABS, polyamide and MF resins, PF resins and epoxy resins.
Examples of final products of the shaped product are serving trays, washing-up basins, crockery, doors, kitchen worktops, furniture, wall panels.
Examples of end products where the shaped product is used as protective layer for a wooden core are worktops having, for example, an acute angle, (kitchen) cupboards particularly the fronts of (kitchen) cupboards consisting of for example milled MDF (= medium density fibre board) or window frames. Examples of articles in which the shaped product serves as protective layer for a plastic core are bumpers, petrol tanks, garden furniture, worktops or car bodywork components.
The protective layer may be glued to the core material. Another possibility is that the shaped product is applied to the core while the resin is still incompletely cured. The resin then serves as glue joint when it is subsequently cured. Then curing and deformation takes place in one process step.
The invention will be described by means of the following, non-limiting examples.
Examble 1 Preparation of resin In a reactor, 24 parts of water and 135 parts of formaldehyde (30% formaldehyde in water adjusted to a pH of 9.3 using 50% NaOH) were added to 100 parts of melamine. The F/M ratio of the resin was 1.7 (F/M ratio is the formaldehyde-melamine molecular ratio). The condensation reaction was performed at 95°C
until the water dilutability of the resin at 2D°C was 1.5 g of resin per g of water. The water dilutability is the amount (g) of water which can be added to a resin solution (g) at 20°C before the solution becomes turbid.
The resin was made reactive (catalyzed) with a 50% (by weight) p-toluenesulphonic acid solution to a pH of 8.1.
Four 10 by 10 cm sheets of Solupor (type 16P03; DSM) were impregnated at room temperature with the above-mentioned resin solution, to which 1% (m/m) of Nonidet~ P40 (Sigma Chemie) had been added as wetting agent. After a few minutes, the sheets impregnated with resin were removed from the resin set-up and the excess resin was removed with the aid of a "wringer". The sheets were dried in a ventilated oven for 4 minutes at 100°C.
Resin content: the resin content of the prepreg was determined by weighing the prepreg and the polymer carrier and was 440%. The resin content is defined as:
(g (prepreg) -g (polym) ) /g (polym) , g(prepreg) and g(polym) are the weights of the prepreg and of the Solupor polymer carrier, respectively.
Residual volatility content: the residual volatility content was determined by measuring the weight loss after drying and curing the prepreg further - ii -for 7 minutes in an oven at 160°C and was 3.5%. The residual volatility content is defined as:
(g (before) -g (after) ) /g (before) , g (before) and g (after) are the weights of the prepreg before and after treatment at 16o°C, respectively.
Resin content: the resin content of the laminate was determined by weighing the laminate and the starting polymers and was 406%. The resin content is defined as:
(g (laminate) -g (polym) ) /g (polym) , g(laminate) and g(polym) are the weights of the laminate and of the polymer carrier, respectively.
Elongation at break: the elongation at break was measured on test pieces (dimensions 4.0*50.0*0.07 mm) at 140°C with the aid of a standard Zwick tensile test bench in accordance with ISO 37 type 3 and was more than 400%, the maximum value measurable with said equipment.
The tensile strength was 5.4 MPa. The rate of deformation was 100 mm/min.
- 2D pressing:
Four 10*10 cm sheets of the prepreg were pressed into a laminate by the following high-pressure laminate pressing cycle: the sheets are placed in the press (of the type Fontijnen SRA 100) at 60°C and the press is brought to a pressure of 80 bar and the press is further heated in approximately 15 minutes to 130°C, said temperature is maintained for 30 minutes and then cooling to 60°C takes place in approximately 15 minutes, after which the pressure is let down.
- 3D pressing:
A few sheets of Solupor prepreg were pressed on a high-density polyethylene core material in an S-shaped mould at 140°C for 20 minutes. The mould clamping force was 9 MPa. Cooling was then carried out for 10 minutes to 40°C. The results are further reported in Tables 1 and 2.
Example 2 The process of Example 1 was repeated, but Tyvek L1058D (DuPont) was used instead of Solupor.
Table 1 shows the resin content, the residual volatility content, the pressing conditions of the prepreg and the resin content of the laminate. Table 2 shows the elongation at break and the tensile strength of the prepreg at the stated test temperature.
The process of Example 1 was repeated, but Lutrasil~ 3450 (Freudenberg) was used instead of Solupor. See Tables 1 and 2 for further conditions and results.
l0 Laminar prepregs comprising a plurality of mutually stacked layers of a-cellulose impregnated with the reaction product of formaldehyde and melamine are disclosed, for example, in US-A-3730828. According to said patent publication, paper is first impregnated with a melamine-formaldehyde resin. Then a prepreg is made by precuring layers and thereafter stacking a few layers of said impregnated paper on top of one another. The resin is then cured in a press under a pressure of, for example, 6 MPa and at a temperature of approximately 150°C. The conversion of the reaction between formaldehyde and melamine in the laminar product thus obtained is complete (completely cured). The laminar products described in said patent publication appear to have good postforming properties. Postforming is understood as meaning that the laminar product can be bent at an elevated temperature which is between 160 and 180°C, it being possible to bend the laminar product along one axis without the laminar product breaking/cracking.
A disadvantage is that, starting from a prepreg according to US-A-3730828, it is not possible to WO 99/13000 PCT/NL9$/00469 obtain laminar products which can be bent into complex shapes along two (or more) mutually intersecting axes without breaking/cracking. Complex shapes may be considered to be, for example, a saddle-type pattern, a small tub, a sickle pattern or a satchel.
The object of this invention is a prepreg with which more complex shapes can be obtained.
This object is achieved in that the carrier is a laminar porous polymer and in that the elongation at break of the prepreg and of the separate impregnated carrier is greater than 10%.
It has been found that, proceeding from the prepreg according to the invention, laminar products can be made in the most diverse shapes without cracks occurring in the laminar product during the deformation.
Laminar products are now possible which have shapes in which the prepregs are locally stretched from lo% to more than 400% during the shaping. A further advantage is that the further curing of the resin and the deformation can be performed in one step. This is in contrast to the method described in the above-mentioned US-A-3730828 where, proceeding from the prepreg, two steps are necessary to arrive at a shaped final product.
An additional advantage is that the prepreg can be processed by a multiplicity of techniques, as a result of which the most optimum technique can be used for each final p=oduct.
Proceeding from the prepreg according to the invention, it is furthermore possible to make laminar products which are bent into an acute angle, for example along one axis. Proceeding from the known prepregs based . . _ 3 _ on a paper carrier, this is impossible.
JP-A-7002119 discloses a prepreg made up of a carrier of a polyamide nonwoven material and a carrier of kraft paper, which carriers are impregnated with a melamine-formaldehyde resin. An impregnated polyamide nonwoven carrier has, as a rule, an elongation at break of more than 10%. However, impregnated kraft paper has an elongation at break of less than 10%, as a result of which the elongation at break of the prepreg as a whole is less than 10%.
A laminar porous polymer carrier is understood as meaning any polymer which comprises a high degree of porosity. The porosity of the polymer carrier is essential for obtaining the advantageous properties of the prepreg as described above.
As a result of the high porosity, the laminar polymer carrier can, as it were, be mixed almost homogeneously with the resin. Preferably, the porosity is obtained in the form of microscopically small, mutually communicating cavities and there are preferably few larger cavities and holes present. Larger holes result in loss of resin during the further processing of the prepreg to its final shape. Preferably, the porosity is sufficiently high for at least 30% by volume of the final shaped part to consist of resin. The porosity is the ratio between the density of the porous polymer carrier with respect to that of the corresponding bulk polymer (no cavities).
The porous polymer carrier may, for example, be a nonwoven laminar polymer, a laminar open polymer foam or a microporous membrane. Preferably, the fibres of the nonwoven are smaller than 0.1 mm. Nonwovens having very small-diameter fibres are also referred to as open films. This class of nonwovens has, as a result of the small thread diameter, few larger meshes and many microscopically small, mutually communicating cavities.
The fibres of said nonwovens lie, as a rule, parallel to the plane of the laminar porous polymer. Polymer foams inherently have a reasonably definable and uniform size of the mutually communicating cavities. The cavities l0 preferably have a diameter of less than 1 mm. Larger cavities may occasionally be present in the foam provided more than 80% by volume of the cavities have said smaller diameters.
The porous polymer carrier may in principle be any porous polymer which meets the requirement that the impregnated carrier has an elongation at break of more than 10%. Examples of porous polymers are porous polyethylene, porous polypropylene, porous polystyrene, porous ethylene/propylene copolymers, porous EPDM, porous polyamides, for example, porous nylon 6,6, porous nylon 6, porous ethylcellulose, porous cellulose acetates, for example porous cellulose diacetate, porous SMA/SAN, porous polyesters, for example porous polyethylene terephthalate (PET), porous polybutylene terephthalate (PBT), porous polyethers. Also possible are combinations of different porous polymers or combinations of porous polymers with paper. As porous polymer carrier, the above-mentioned polymers can be used as nonwoven, open film or open polymer foam.
Examples of an open-film polyethylene are the polyethylene types which are known under the name of Solupor (Solupor is a DSM N.V. brand name). Nonwovens based on various polymers are suitable to be used as carrier. An example of a nonwoven polyethylene is Tyvek (Tyvek~ is a DuPont de Nemours brand name). An example of a nonwoven polypropylene is Lutrasil~ (Lutrasil~ is a Freudenberg brand name). An example of a nonwoven polyester is Viledori H1206. An example of a nonwoven polyamide is Viledon FS2118 (Viledon is a Freudenberg brand name). An example of an open polymer foam is Calligan open-cell foam standard 1.17 polyether (Calligari is a Calligan Europe B.V. brand name). An example of a cellulose filled nonwoven polypropylene is Workhouses (Workhouses is a Kimberly-Clark brand name).
An example of a nonwoven cellulose acetate is TAT 2121 which is a product of Freudenberg.
The polymer may have either polar or apolar properties. As a result of making use of suitable wetting agents, the desired degree of impregnation of the polymer sheet by the resin can be obtained. As a rule, all the wetting agents known to the person skilled in the art can be used. Examples of wetting agents are PAT 523W, PAT 959 (PAT is a Wiirtz brand name), Nonidet~ P40 (Nonidet~ P40 is a Sigma Chemie brand name) and Aminol~ N (Aminol~ is a Chem-Y brand name).
The resin may in principle be any known thermosetting resin. Examples are aminoplast formaldehyde resin, phenol-formaldehyde resin (PF
resin), epoxy resin or unsaturated polyester resin.
Preferably, an aminoplast-formaldehyde resin is used as resin. Urea, melamine or benzoguanamine, for example, can be used as aminoplast. Preferably, melamine is used because of its superior mechanical properties.
The resin can be prepared in a process known to the person skilled in the art by reacting aminoplast and formaldehyde in water. The ratio of, for example, formaldehyde:melamine is normally speaking between 1:1 and 6:1, preferably between 1.2:1 and 2:1. Optionally, the aminoplast can be partially replaced by, for example, phenol, but this may have adverse effects on the colour. Modifiers, such as sorbitol, s-caprolactam, l0 ethylene glycol, trioxitol, toluenesulphonamide, and benzo- and acetoguanamine can also be added.
Mechanical properties which can be used well in practice are achieved if 10-70% by weight of porous polymer and 90-30% by weight of resin are used. The resin may contain the known fillers such as lime, clay, glass, carbon, silica or metal particles. It has been found, however, that the best results are achieved in the absence of fillers or at any rate with less filler than has been usual hitherto. The filler and resin weight ratio is preferably between 0:1 and 0.5:1. These ratios relate to the cured, final laminar product.
The prepreg comprises one or more stacked sheets of the impregnated porous polymer carrier. The number of laminar carriers is, as a rule, 10 or lower, and preferably 5 or lower. The thickness of the prepreg can vary from 100 ~m to approximately 3 cm. The degree to which the resin is cured in the prepreg can be determined for melamine-formaldehyde (MF) and PF resins by determining the residual volatility. Said residual volatility is the loss in mass of the prepreg during 7 minutes at 160°C. The residual volatility of the prepreg is, as a rule, between 2 and 20%. The elongation at break of the prepreg as used in the description is defined as the elongation at break for a residual volatility of approximately 5%.
The prepreg is made under the conditions which are already known for making prepregs based on a paper carrier, as described, for example, in the above-mentioned US-A-3730828 or JP-A-7002119. The resin is preferably dissolved in water and is water-fluid , the resin preferably having a viscosity of 1-1000 Pa.s. The viscosity can be influenced by varying the amount of solvent. The solvent will vary depending on the chosen resin. Still uncured aminoplast-formaldehyde is preferably dissolved in water. Preferably solvents are used in which the polymer carrier does not dissolve or swell. The temperature during the impregnation may be between 15 and 60°C and, for practical reasons, is often room temperature. Higher temperatures are less practical because the resin partially cures during the impregnation. The pressure during the impregnation is not critical and, for practical reasons is, as a rule, atmospheric.
The carriers impregnated in this way are dried until the residual volatility is reached, as described above for the prepreg. The drying preferably takes place at a temperature of 100-160°C. Higher temperatures are less practical because the drying times then become too short, resulting in a less controllable process. The temperature will in practice also be determined by the type of oven. Preferably, the carrier is stacked after the drying.
WO 99/13000 PCT/NL98/004b9 _ _ g _ The elongation at break of the separate impregnated carrier (residual volatility = approximately 5%) and of the prepreg obtained is greater than 10% and preferably greater than 50%. The prepreg may optionally also comprise layers of a non-porous polymer in addition to the porous polymer carriers provided these polymers also have an elongation at break which is greater than or equal to that of the prepreg.
The prepreg can be processed into a shaped final product by first deforming the prepreg and then curing the shaped intermediate product at elevated temperature or by combining the deformation and the curing in one step.
The deformation, optionally in combination with the curing, can be performed by means of bending, embossing, stamping, pneumatically stretching or mechanically 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 begins to flow. Said yield stress is determined by the resin composition, resin content, polymer type and water content. In principle, said temperature may be between room temperature and 200°C. At temperatures higher than 100°C, the resin will already (partially) cure during the deformation, as a result of which the deformation and curing of the resin will take place simultaneously.
The shaped product obtained in this way can be used as final product or as protective layer around an object having a core material of, for example, wood, metal, glass or plastic, for example polyethylene, _ _ 9 polypropylene, ABS, polyamide and MF resins, PF resins and epoxy resins.
Examples of final products of the shaped product are serving trays, washing-up basins, crockery, doors, kitchen worktops, furniture, wall panels.
Examples of end products where the shaped product is used as protective layer for a wooden core are worktops having, for example, an acute angle, (kitchen) cupboards particularly the fronts of (kitchen) cupboards consisting of for example milled MDF (= medium density fibre board) or window frames. Examples of articles in which the shaped product serves as protective layer for a plastic core are bumpers, petrol tanks, garden furniture, worktops or car bodywork components.
The protective layer may be glued to the core material. Another possibility is that the shaped product is applied to the core while the resin is still incompletely cured. The resin then serves as glue joint when it is subsequently cured. Then curing and deformation takes place in one process step.
The invention will be described by means of the following, non-limiting examples.
Examble 1 Preparation of resin In a reactor, 24 parts of water and 135 parts of formaldehyde (30% formaldehyde in water adjusted to a pH of 9.3 using 50% NaOH) were added to 100 parts of melamine. The F/M ratio of the resin was 1.7 (F/M ratio is the formaldehyde-melamine molecular ratio). The condensation reaction was performed at 95°C
until the water dilutability of the resin at 2D°C was 1.5 g of resin per g of water. The water dilutability is the amount (g) of water which can be added to a resin solution (g) at 20°C before the solution becomes turbid.
The resin was made reactive (catalyzed) with a 50% (by weight) p-toluenesulphonic acid solution to a pH of 8.1.
Four 10 by 10 cm sheets of Solupor (type 16P03; DSM) were impregnated at room temperature with the above-mentioned resin solution, to which 1% (m/m) of Nonidet~ P40 (Sigma Chemie) had been added as wetting agent. After a few minutes, the sheets impregnated with resin were removed from the resin set-up and the excess resin was removed with the aid of a "wringer". The sheets were dried in a ventilated oven for 4 minutes at 100°C.
Resin content: the resin content of the prepreg was determined by weighing the prepreg and the polymer carrier and was 440%. The resin content is defined as:
(g (prepreg) -g (polym) ) /g (polym) , g(prepreg) and g(polym) are the weights of the prepreg and of the Solupor polymer carrier, respectively.
Residual volatility content: the residual volatility content was determined by measuring the weight loss after drying and curing the prepreg further - ii -for 7 minutes in an oven at 160°C and was 3.5%. The residual volatility content is defined as:
(g (before) -g (after) ) /g (before) , g (before) and g (after) are the weights of the prepreg before and after treatment at 16o°C, respectively.
Resin content: the resin content of the laminate was determined by weighing the laminate and the starting polymers and was 406%. The resin content is defined as:
(g (laminate) -g (polym) ) /g (polym) , g(laminate) and g(polym) are the weights of the laminate and of the polymer carrier, respectively.
Elongation at break: the elongation at break was measured on test pieces (dimensions 4.0*50.0*0.07 mm) at 140°C with the aid of a standard Zwick tensile test bench in accordance with ISO 37 type 3 and was more than 400%, the maximum value measurable with said equipment.
The tensile strength was 5.4 MPa. The rate of deformation was 100 mm/min.
- 2D pressing:
Four 10*10 cm sheets of the prepreg were pressed into a laminate by the following high-pressure laminate pressing cycle: the sheets are placed in the press (of the type Fontijnen SRA 100) at 60°C and the press is brought to a pressure of 80 bar and the press is further heated in approximately 15 minutes to 130°C, said temperature is maintained for 30 minutes and then cooling to 60°C takes place in approximately 15 minutes, after which the pressure is let down.
- 3D pressing:
A few sheets of Solupor prepreg were pressed on a high-density polyethylene core material in an S-shaped mould at 140°C for 20 minutes. The mould clamping force was 9 MPa. Cooling was then carried out for 10 minutes to 40°C. The results are further reported in Tables 1 and 2.
Example 2 The process of Example 1 was repeated, but Tyvek L1058D (DuPont) was used instead of Solupor.
Table 1 shows the resin content, the residual volatility content, the pressing conditions of the prepreg and the resin content of the laminate. Table 2 shows the elongation at break and the tensile strength of the prepreg at the stated test temperature.
The process of Example 1 was repeated, but Lutrasil~ 3450 (Freudenberg) was used instead of Solupor. See Tables 1 and 2 for further conditions and results.
3 0 Examp; a 4 The process of Example 1 was repeated, but cellulose diacetate (CD) nonwoven was used instead of Solupor. See Tables 1 and 2 for further conditions and results.
Example 5 The process of Example 1 was repeated, Viledon FS2118 being used instead of Solupor~. See Tables 1 and 2 for further conditions and results.
Example 6 The process of Example 1 was repeated, Viledon H1206 being used instead of Solupo= . See Tables 1 and 2 for further conditions and results.
Co~arison Experiment A
The same process as in Example 1 was used, but a decorative paper (80 g/m2) was used instead of Solupor. See Tables 1 and 2 for further conditions and results.
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Example 5 The process of Example 1 was repeated, Viledon FS2118 being used instead of Solupor~. See Tables 1 and 2 for further conditions and results.
Example 6 The process of Example 1 was repeated, Viledon H1206 being used instead of Solupo= . See Tables 1 and 2 for further conditions and results.
Co~arison Experiment A
The same process as in Example 1 was used, but a decorative paper (80 g/m2) was used instead of Solupor. See Tables 1 and 2 for further conditions and results.
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Claims (14)
1. Laminar prepreg comprising one or more layers of a laminar carrier, which carrier is impregnated with an as yet uncured resin, characterized in that the carrier is a laminar porous polymer and in that the elongation at break of the prepreg and of the separate impregnated laminar carrier is greater that 10% in accordance with ISO 37 and for a residual volatility of approximately 5%.
2. Laminar prepreg according to Claim 1, characterized in that the elongation at break of the separate impregnated laminar carrier and of the prepreg is greater than 50%.
3. Laminar prepreg according to one of Claims 1-2, characterized in that the density of the porous polymer carrier is less than 70% of the density of the corresponding bulk polymer.
4. Laminar prepreg according to one of Claims 1-3, characterized in that the porous polymer carrier is a laminar nonwoven, open-film or open-foam polymer carrier.
5. Laminar prepreg according to Claim 4, characterized in that the porous polymer carrier is a nonwoven or open-film carrier.
6. Laminar prepreg according to one of Claims 1-5, characterized in that the resin is an aminoplastic formaldehyde resin, a phenol-formaldehyde resin, an epoxy resin or an unsaturated polyester resin.
7. Laminar prepreg according to Claim 6, characterized in that the resin is an aminoplastic formaldehyde resin.
8. Laminar prepreg according to Claim 7, characterized in that the aminoplastic is urea, melamine or benzoguanamine.
9. Laminar prepreg according to one of Claims 7-8, characterized in that the residual volatility is between 2 and 20%.
10. Laminar prepreg according to one of Claims 1-9, characterized in that the filler and resin weight ratio is between 0:1 and 0.5:1.
11. Method of making a prepreg according to one of Claims 7-9, the polymer carrier being impregnated with water-fluid resin, optionally in the presence of a wetting agent, after which the carriers impregnated in this way are dried (precured), with the water being evaporated, so that the prepreg has a residual volatility of 2-20%, after which stacking of the prepreg is optionally carried out.
12. Method for the processing of a prepreg according to one of Claims 1-10 into a shaped product, the prepreg being deformed at a temperature between room temperature and 200°C with the resin being cured either in a subsequent step or during the deformation.
13. Method according to Claim 12, characterized in that the prepreg has locally been stretched at least 50%
during the shaping.
during the shaping.
14. Use of the shaped product obtained by the method according to one of Claims 12-13 as protective layer for a wooden, plastic, glass or metal object.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1007001A NL1007001C2 (en) | 1997-09-11 | 1997-09-11 | Sheet-shaped prepreg. |
NL1007001 | 1997-09-11 | ||
PCT/NL1998/000469 WO1999013000A1 (en) | 1997-09-11 | 1998-08-19 | Laminar prepreg |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2302618A1 true CA2302618A1 (en) | 1999-03-18 |
Family
ID=19765655
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002302618A Abandoned CA2302618A1 (en) | 1997-09-11 | 1998-08-19 | Laminar prepreg |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP1021482A1 (en) |
JP (1) | JP2001515940A (en) |
KR (1) | KR20010023747A (en) |
CN (1) | CN1269813A (en) |
AU (1) | AU736091B2 (en) |
CA (1) | CA2302618A1 (en) |
EA (1) | EA200000307A1 (en) |
ID (1) | ID25796A (en) |
NL (1) | NL1007001C2 (en) |
NO (1) | NO20001268L (en) |
PL (1) | PL339228A1 (en) |
WO (1) | WO1999013000A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104553177B (en) * | 2014-12-15 | 2017-01-04 | 中航复合材料有限责任公司 | A kind of flame-retardant modified carbon fiber prepreg and composite product |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4601944A (en) * | 1985-06-05 | 1986-07-22 | Westinghouse Electric Corp. | Polybutadiene-epoxy-anhydride laminating resins |
KR950005536A (en) * | 1993-08-05 | 1995-03-20 | 사또오 아키오 | Prepregs and Laminated Structures |
EP0768334B1 (en) * | 1995-10-16 | 2004-02-18 | Sumitomo Chemical Company Limited | Prepreg, process for producing the same and printed circuit substrate using the same |
-
1997
- 1997-09-11 NL NL1007001A patent/NL1007001C2/en not_active IP Right Cessation
-
1998
- 1998-08-19 PL PL98339228A patent/PL339228A1/en unknown
- 1998-08-19 CA CA002302618A patent/CA2302618A1/en not_active Abandoned
- 1998-08-19 WO PCT/NL1998/000469 patent/WO1999013000A1/en not_active Application Discontinuation
- 1998-08-19 AU AU88895/98A patent/AU736091B2/en not_active Ceased
- 1998-08-19 ID IDW20000457D patent/ID25796A/en unknown
- 1998-08-19 EA EA200000307A patent/EA200000307A1/en unknown
- 1998-08-19 EP EP98940673A patent/EP1021482A1/en not_active Withdrawn
- 1998-08-19 JP JP2000510798A patent/JP2001515940A/en active Pending
- 1998-08-19 KR KR1020007002402A patent/KR20010023747A/en not_active Application Discontinuation
- 1998-08-19 CN CN98809004A patent/CN1269813A/en active Pending
-
2000
- 2000-03-10 NO NO20001268A patent/NO20001268L/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
NO20001268D0 (en) | 2000-03-10 |
WO1999013000A1 (en) | 1999-03-18 |
AU736091B2 (en) | 2001-07-26 |
CN1269813A (en) | 2000-10-11 |
JP2001515940A (en) | 2001-09-25 |
EA200000307A1 (en) | 2000-08-28 |
NL1007001C2 (en) | 1999-03-12 |
ID25796A (en) | 2000-11-02 |
PL339228A1 (en) | 2000-12-04 |
AU8889598A (en) | 1999-03-29 |
NO20001268L (en) | 2000-05-11 |
EP1021482A1 (en) | 2000-07-26 |
KR20010023747A (en) | 2001-03-26 |
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