WO1993016856A1 - Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same - Google Patents
Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same Download PDFInfo
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- WO1993016856A1 WO1993016856A1 PCT/US1992/001391 US9201391W WO9316856A1 WO 1993016856 A1 WO1993016856 A1 WO 1993016856A1 US 9201391 W US9201391 W US 9201391W WO 9316856 A1 WO9316856 A1 WO 9316856A1
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- WO
- WIPO (PCT)
- Prior art keywords
- mold
- coating
- thermoplastic resin
- substrate
- high modulus
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
- B29C70/086—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers and with one or more layers of pure plastics material, e.g. foam layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/902—High modulus filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2904—Staple length fiber
- Y10T428/2905—Plural and with bonded intersections only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/659—Including an additional nonwoven fabric
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/697—Containing at least two chemically different strand or fiber materials
Definitions
- the present invention relates to providing recyclable high modulus fiber reinforced composite structures having an enhanced surface appearance.
- a long standing problem in providing reinforced composite structures resides in manufacturing structures which when painted provide a Class A finish. These structures such as automotive body panels must be capable of being processed in assembly plants with steel panels. They must be able to survive assembly plant conditions, painting and baking, where maximum metal temperatures can reach 200°C for as long as 30 minutes with surface coatings remaining firmly adherred to the substrate and retaining their Class A appearance.
- the body panels must have, after processing,, an appearance that is comparable to the appearance of an adjoining part made of steel.
- thermosetting SMCs are not recyclable in the sense that they cannot be remelted or depolymerized.
- the products of this invention which solve the problems noted above are made by preparing composite structures comprised of a substrate prepared from a plurality of layers of a self-supporting porous web comprised of randomly dispersed high modulus reinforcing fibers held together by solidified thermoplastic resin.
- the layers are heated-t ⁇ i ⁇ jvi__r ⁇ -pr €___old form which is then placed in a mold to flow.'sblidify, and crystallize the thermoplastic resin.
- the resulting reinforced thermoplastic substrate is coated in the mold with a thin coating of a thermosetting resin-containing composition.
- the layers of porous web are stacked together to form a batt which is heated in a convection oven to convert the batt into a moldable form.
- the number of layers is determined by weighing the precut shapes to provide a predetermined mold charge mass which is based on the final desired molded part thickness.
- the moldable form is then placed in a heated mold.
- the mold is closed and pressure is applied to flow mold the preform to form a consolidated part and to crystallize the thermoplastic resin component.
- the mold halves are separated and/or the pressure is released to permit introduction of a thermosetting resm-containing coating material.
- the mold is then closed, and under pressure, the material spreads over the surface of the molded preform. Heating under pressure is continued for a time sufficient to set the coating composition.
- the thermosetting composition adheres tenaciously to the reinforced molded thermoplastic substrate and exhibits outstanding surface appearance.
- the batts used to prepare the preforms are comprised of from 5 to 50 percent by weight glass fibers and from 50 to 95 percent by weight thermoplastic resin.
- the batts are air permeable and are made from air permeable webs of randomly dispersed high modulus fibers held together at fiber crossover locations by solidified globules of thermoplastic resin enveloping the fibers at the crossover locations. Some of the randomly dispersed fibers have bead-like drops of solidified thermoplastic resin adhered thereto at locations along their length at locations other than at crossovers.
- the preparation of such webs is disclosed in Geary and Weeks US Patent Application No. 07/606,651, filed October 31, 1990 and European Patent Application 0341 977, published November 15, 1989.
- the products of this invention are composite structures which are warp-free, have very smooth surfaces and exhibit excellent physical properties.
- the thermosetting resin-containing surface coating strongly adheres to the reinforced molded thermoplastic substrate surface.
- the painted surface is rated Class "A".
- the quality of the surface coating can be measured using a commercially available distinctness of image (DOI) meter. Reflected light intensity from a photo detector is measured as a function of the scatterilng angle. If the scattering function is short and wide, the surface is said to have a low DOI. If the scattering is limited, the surface has a high DOI. DOI meters detect the reflected light in a region slightly away from the spectral angle. If the light detected is small, the distinctness is high. DOI is measured on.a scale from 0 to 100 with 100 being the highest level of smoothness.
- Paint procedures which are well known in the art may be used with the structures of this invention. They may be painted side by side with steel parts. For example, the surfaces may be primed and topcoated, or optionally a basecoat/clear coat finish may be applied. When placed in a drying oven after being painted, no "paint pops" occur whereas in using SMCs, due to emission of low molecular weight monomers, "paint pops" are encountered.
- FIG. 1 is a schematic illustration of a cross section of a composite structure produced by the process of this invention.
- Fig. 1 shows reinforced thermoplastic substrate 10 which has been coated with thermosetting resin-containing coating 12. The resulting composite part is coated with multiple layers of paint 14.
- a porous batt is formed from an intimate homogenous blend of reinforcing fiber and thermoplastic resin fiber components.
- the reinforcing fiber may be any high modulus fiber, such as polyamides, glass, carbon, polyesters and high temperature nylons. A modulus of at least 100,000 M Pascals is preferred.
- the reinforcing fibers may be of consistent length or a mixture of variable length fibers. Generally, long fibers in the range of one to eight centimeters are preferred.
- thermoplastic resin fibers may be any thermoplastic or combination of several suitable thermoplastics for the application.
- suitable thermoplastics include, but are not limited to, polyethylene, polypropylene, polyesters, copolyesters, polyamides, including Nylon 6, Nylon 6/6, Nylon 11, Nylon 12, and J2, polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polymethylphenylene, polyarylates and polyvinylidene fluoride.
- the denier and length of the thermoplastic fiber is chosen such that the volume of a single fiber is within a range, preferably between 1.5 x 10"4 to 10 x 10"3 m ⁇ n.3 which when heated results in a globule volume in the range of approximately 0.5 x 10"4 to 1 x 10"3 ⁇ UT
- the thermoplastic fiber diameter is generally chosen based on economic considerations.
- the most economical polyester staple is 1.5 denier per filament (DPF). In general, a length of 1-50 mm and DPF of greater than 0.5 is preferred.
- An intimately blended web if formed from the high modulus • and thermoplastic fibers.
- the basis weight of the formed web is in the range of 0.05 - 0.2 pounds per square foot (0.244 - 0.98 kg/sq m).
- the formed web is passed through a convection heating oven to dry and melt the thermoplastic fiber forming globules which bond the structure together. This melting step produces a web of substantial strength sufficient for normal web handling and is critical to obtaining a web that has the high porosity desired for subsequent convection heating in preparation for molding.
- thermosetting resin-containing coating compositions are unsaturated resins which are rendered insoluble and infusible by cross- linking.
- Such resins are well known in the art and can be of the type disclosed by Sorenson and Campbell in Chapter 7, "Synthetic Resins", published by INTERSOENCE PUBLISHERS, INC., New York, 1961.
- Examples include polyester/acrylic/vinyl monomer resins. The various combinations of polyester, acrylic and vinyl monomers are very great. Also various alkyd and unsaturated polyester resins described in MODERN PLASTICS ENCYCLOPEDIA, 1989 Edition,published by Mc Graw Hill, New York, may be used.
- thermosetting coating compositions can be filled or compounded to give the desired viscosity and flow characteristics for molding and to afford the desired physical properties in the resulting coating.
- fillers or compounding ingredients are fillers like clay, talc, magnesium oxide, magnesium hydroxide, calcium carbonate and calcium silicate, mold release agents, colorants such as red iron oxide, titanium oxide, carbon black, organic color pigments such as phthalocyanine blue or green, antidegradants, UV absorbers, calcium silicate, hollow glass or resin micro ⁇ spheres, thickening agents, inhibitors and the like. Care should be exercised in the use of high filler contents as this may give high viscosities and result in flow and handling difficulties.
- a preferred thermosetting resin-containing composition consists of a styrene containing modified acrylic resin mixture which is sold by GenCorp Inc. under the trademark Genglaze ® .
- a preferred reinforcing fiber used in the invention is glass fiber which consists of conventional spun glass strand having a diameter between 5 and 50 microns and a cut length of 1 to 8 cm. As is common in the industry, such glass is sized and chopped to length and shipped "wet" in moisture proof containers to the customer.
- a preferred material is that sold by Owens- Corning Fiberglass (OCF) under the label 133A.
- the preferred molding method for practicing the invention is compression molding.
- a stack of sheets are layered together.
- the stack is placed in a forced air convection oven and heated above the melting point of the thermoplastic resin component for less than one minute.
- the heated preform is then placed in a compression mold where the tool temperature is adjusted to a temperature to crystallize the thermoplastic resin component.
- Sufficient pressure is applied to flow mold the preform to fill out the mold.
- a dwell time preferably 30 to 60 seconds the mold is opened.
- a thermosetting resin-containing component is introduced into the mold in an amount sufficient to create a layer from 3 to 10 mils (0.076 to 0.254 mm) thick over the upper surface of the preform.
- the coated structure is held in the mold under pressure for a time sufficient to cure the thermosetting resin-containing component.
- the coated structure is permitted to cool sufficiently for handling and is then removed from the mold.
- compression molding the mold must be opened enough to place the charge of coating composition in the mold on the surface to be coated.
- injection molding the mold is opened enough to insert the charge means, i.e. opening it by an amount equal to the desired thickness of the coating, to permit injection of the component, or injection may be made against the pressure in the mold.
- a porous web of the type described above comprised of glass fiber and polyethylene terephthalate (PET) fiber is precut into a predetermined shape.
- Several layers of the precut material, (15-25 layers) are stacked together to make up a molding charge.
- the molding charge is then placed in a specially designed convection oven where the thermoplastic resin is remelted.
- the preheating is accomplished with an air temperature of from 285 -320°C and requires 30-90 seconds.
- the flow (velocity) of heated air through the charge is in the range from 150 to 400 feet per minute (45.72 to 121.92 meters per minute) which for an average thickness mold charge will create a pressure drop through the thickness of the charge of less than 7 inches of water.
- the molding charge is removed from the oven and placed in a compression mold.
- the mold surface temperature is typically between 150-175°C when using polyethylene terephthalate resin.
- the charge size is typically between 40 and 100% of the planform area of the part to be molded.
- a tool presssure of 2000 psi (13.8 M pascals) or greater should be achieved which is typically maintained through the duration of the part forming step.
- Mold dwell is typically 30-60 seconds depending on the thickness of the part.
- thermosetting resm-containing material Upon completion of the part forming step, surface enhancement is achieved through use of in-mold-coating using a thermosetting resm-containing material. As disclosed above, the coating can be done manually or by automated injection.
- the mold halves are separated upon completion of the part forming process. It is essential at this stage that the surface of the molded part be free of debris, e.g. molding flash.
- the in-mold- coating is premixed with a catalyst and then poured onto the part surface to be coated.
- the amount of coating used is typically 0.06 to 0.22 grams per square inch (0.0093 to 0.0341 gm/sqcm) of part surface to be coated. This will give a coating thickness from 3 to 10 mils (0.076 to 0.254 mm).
- the mold is then closed, and a tool pressure of not more than 1000 psi (6.9 M pascals), 500-800 psi is optimal, (3.5 M - 5.5 M pascals) is achieved. This tool pressure flows the in-mold coating over the surface of the molded part.
- the mold dwell is 15-60 seconds depending on the particular coating system used.
- the mold is then opened, and the part is removed.
- the composite part can be assembled with steel parts and painted using well known procedures.
- suitable paint compositions which may be used are those disclosed in U.S. Patents 4,816,500, U.S.4,954,559 and U.S.5,051,209. .
- the pressure is relieved, and the mold halves are separated slightly.
- Precatalyzed coating composition is then injected through an injector port across the surface of the tool. Again, the same rule for the amount of coating applies.
- the mold is closed to a tool pressure of not more than 1000 psi (6.9 M pascals), and the mold dwell time is again 15- 60 seconds depending on the particular type of coating composition used. The mold is then opened and the part removed.
- the process of the invention can be used to mold automobile parts such as grille and headlamp assemblies, deck hoods, fenders, door panels and roofs as well as in the manufacture of various plastic articles such as food trays, appliance and electrical components and in other applications where surface smoothness is required for subsequent application of paint.
- thermoplastic products of this invention are recyclable.
- properties of recovered thermoplastic products are not adversely affected by the presence of the thermosetting resm-containing coatings.
- the invention will be further illustrated by the following examples in which parts and percentages are by weight unless otherwise indicated. Units reported throughout the specification and claims in SI units have been converted from the English system to the SI System.
- a self-supporting porous batt was prepared from polyethylene terephthalate fiber (PET) having an as spun denier of 1.5.
- PET polyethylene terephthalate fiber
- the fiber was coverted to a staple length of 1/4 inch (0.635 cm) and intimately mixed with 1 inch long glass fiber having a diameter of about 0.5 mil (0.013 mm).
- the above ingredients were slurried in water and directed to a moving belt from a paper machine head box, then to a dryer.
- the mat consisted of 40.7 Wt. % glass fiber (Owens Corning Fiberglass "K” ) 57.2 Wt. % PET fiber and 9.1 Wt.
- % of a lower melting copolyester binder fiber Ciba Geigy's antioxidant, Irganox ® 1010 was added to the slurry in an amount of 1.0 Wt. %.
- a belt speed of 22 fpm (6.71 mpm) and heater temperature of 195°C was used to partially melt the PET fiber.
- a batt having a basis weight of about 0.171 lb/sqft (8.35 kq/sqcm) and a consistency of 0.54 Wt. % was obtained.
- the batt was placed in a convection oven and heated at a temperature of 285°C for 30 seconds while circulating hot air through the batt at about 350 feet per minute (106.68 m/min) to melt the PET component.
- the batt was then placed in a compression mold for 1 minute at a temperature of 150-180°C to crystallize the structure. Mold pressure was controlled at between 1,500 and 2,500 psi (10.34 and 17.24 M pascals). The mold was opened to expose the exterior surface of the molded structure.
- thermosetting ' styrene containing modified acrylic resinous coating material sold by GenCorp Inc. under the trademark GENGLAZE ® EC 600 was applied to the exposed surface of the molded structure in an amount of 0.14 gram/square inch (217.95 gm/sqm)
- the mold was reclosed under partial vacuum at a lower pressure of about 200 to 1000 psi (1.4 to 6.9 M pascals) to distribute the coating material over the surface of the molded structure.
- the mold was opened and the coated structure was removed.
- the coating was uniformly distributed, having a thickness of 6 mils, with a very smooth surface
- Example 2 The procedure described in Example 1 was repeated except that the glass fiber content of the batt was reduced to 25 wt. %, no binder fiber was used, the polyethylene terephthalate fiber content was increased to 75 wt. % and Ciba Geigy's antioxidant, Irganox ® 1330, was used in an amount of 0.25 wt. %, the belt speed was increased to 25 fpm (7.62 m/m) and the heater temperature was increased to 280°C.
- the sheet having a basis weight of 0.091 lb/sqft (0.444 kg/sqm).
- a clicker die was used to convert the rolled batt into a form suitable for thermal compression molding.
- a preform consisting of twenty (20) sheets stacked as a batt gave a part weight of about 1.0 to 1.5 lbs/sqft (0.488 to 0.732 gm/sqcm) on thermal compression molding.
- the batt was placed in a convection oven and hot air was circulated through the batt at about 350 ft/min (106.68 m/min) for 30 seconds at 285°C to convert the porous batt into a moldable form.
- the pliable melt was placed into a mold for one minute at a mold temperature of 150 to 180°C to produce a crystallized structure.
- the mold pressure was controlled at 2000 psi (13.8 M pascals).
- a resinous coating material consisting of GENGLAZE ® EC 600 was apphed to the exposed surface of the molded structure in an amount of 0.14 grams/sq inch (217.95 gn/sqm).
- the mold was reclosed under partial vacuum at a lower pressure of about 200 to 1000 psi (1.4 to 6.9 M pascals) to distribute the coating material over the surface of the molded structure.
- the coating had a thickness of 6 mils (0.152mm) A very smooth coated surface was obtained.
- Products prepared by the process of this invention were tested using a Bendix Surface Profilometer, Model No.21, stylus head Bendix T-231 and probe diameter of 0.0004 inch (0.01016 mm) to determine the surface roughness. Products of this invention were found to have a maximum surface roughness deviation of less than 50 micro-inches (0.00127 mm) over a 0.25 inch (6.35 mm) span.
- thermosetting resm-containing coating Adhesion of the thermosetting resm-containing coating to the thermoplastic substrate was tested using an Instron tensile tester. Two metal cylinders having a diameter of 1.596 inches (4.05 cm),2 sq inches surface area,(12.9 sqcm) were bonded using Dexter Hysol ® adhesive, EA 934NA, a two part past adhesive, to each side of a test sample. When the adhesive was cured, the pieces were pulled apart in the Instron tester. The test samples were prepared by the process described in the Examples. The results of the tests are set forth in the following Table: MATERIAL STRENGTH TYPE OF FAILURE
- adheresion value means the tensile strength of the bond between the surface coating and the substrate as measured using an Instron tensile tester, Model No.1127, using a 25,000 kg reversible load cell, or equivalent, and reported in psi (pascals). Products of this invention have adhesion values greater than 1000 psi (6.9 M pascals). This adhesion value must be attained to provide an acceptable product which is useful in industry applications. In conducting tests to determine adhesion values any suitable adhesive which has a bonding strength greater than the force required to delaminate the substrate may be used.
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9207085A BR9207085A (en) | 1992-02-21 | 1992-02-21 | Process of preparing a reinforced recyclable composite structure with improved surface appearance and obtained composite structures |
PCT/US1992/001391 WO1993016856A1 (en) | 1992-02-21 | 1992-02-21 | Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same |
ES92912089T ES2111069T3 (en) | 1992-02-21 | 1992-02-21 | RECYCLABLE HIGH MODULE MOLDED THERMOPLASTIC STRUCTURES, REINFORCED WITH FIBERS AND PROCEDURE TO PRODUCE THEM. |
DE1992623806 DE69223806T2 (en) | 1992-02-21 | 1992-02-21 | RECYCLABLE MOLDED THERMOPLASTIC STRUCTURES REINFORCED WITH HIGH MODULAR FIBER AND METHOD FOR THE PRODUCTION THEREOF |
JP5514782A JPH07503912A (en) | 1992-02-21 | 1992-02-21 | Recyclable molded high modulus fiber reinforced thermoplastic structure and its manufacturing method |
CZ942000A CZ9402000A3 (en) | 1992-02-21 | 1992-02-21 | Recyclable moulded thermoplastic structures reinforced by high-molecular fibers and process for preparing thereof |
CA 2130120 CA2130120A1 (en) | 1992-02-21 | 1992-02-21 | Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same |
AU20140/92A AU2014092A (en) | 1992-02-21 | 1992-02-21 | Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same |
EP19920912089 EP0626901B1 (en) | 1992-02-21 | 1992-02-21 | Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same |
US08/590,959 US5632949A (en) | 1992-02-21 | 1996-01-24 | Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1992/001391 WO1993016856A1 (en) | 1992-02-21 | 1992-02-21 | Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same |
Publications (1)
Publication Number | Publication Date |
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WO1993016856A1 true WO1993016856A1 (en) | 1993-09-02 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1992/001391 WO1993016856A1 (en) | 1992-02-21 | 1992-02-21 | Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same |
Country Status (10)
Country | Link |
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US (1) | US5632949A (en) |
EP (1) | EP0626901B1 (en) |
JP (1) | JPH07503912A (en) |
AU (1) | AU2014092A (en) |
BR (1) | BR9207085A (en) |
CA (1) | CA2130120A1 (en) |
CZ (1) | CZ9402000A3 (en) |
DE (1) | DE69223806T2 (en) |
ES (1) | ES2111069T3 (en) |
WO (1) | WO1993016856A1 (en) |
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EP0933195A1 (en) * | 1997-12-17 | 1999-08-04 | Freistaat Bayern, vertreten durch Friedrich-Alexander-Universität Erlangen-Nürnberg | Fibre-reinforced synthetic structure |
EP3603924A4 (en) * | 2017-06-22 | 2020-04-29 | Mitsubishi Heavy Industries, Ltd. | Method for producing composite material structure |
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JPH08174688A (en) * | 1994-12-21 | 1996-07-09 | Ikeda Bussan Co Ltd | Resin molded form for vehicle |
KR20030007539A (en) * | 2000-04-20 | 2003-01-23 | 데코마 익스테리어 트림 인크. | Method of molding a panel |
US20040071980A1 (en) * | 2000-07-12 | 2004-04-15 | Mcbain Douglas S. | Method for in-mold coating a polyolefin article |
US6793861B2 (en) | 2000-07-12 | 2004-09-21 | Omnova Solutions Inc. | Optimization of in-mold coating injection molded thermoplastic substrates |
US6617033B1 (en) | 2000-07-12 | 2003-09-09 | Omnova Solutions Inc. | Method for in-mold coating a polyolefin article |
US6890469B2 (en) | 2001-10-22 | 2005-05-10 | Omnova Solutions Inc. | Selectively controlling in-mold coating flow |
US6887550B2 (en) * | 2001-10-22 | 2005-05-03 | Omnova Solutions Inc. | Removable defined flange for in-mold coating containment |
US7045213B2 (en) * | 2001-10-22 | 2006-05-16 | Omnova Solutions Inc. | In-mold coating injection inlet flow control |
US7105231B2 (en) * | 2001-10-22 | 2006-09-12 | Omnova Solutions Inc. | In-mold coating barrier for a substrate injection orifice |
US6676877B2 (en) * | 2002-04-03 | 2004-01-13 | Omnova Solutions Inc. | Mold runner for prevention of in-mold coating flow |
US20040121034A1 (en) * | 2002-12-10 | 2004-06-24 | Mcbain Douglas S. | Integral injection molding and in-mold coating apparatus |
US20050266757A1 (en) * | 2003-10-17 | 2005-12-01 | Roekens Bertrand J | Static free wet use chopped strands (WUCS) for use in a dry laid process |
US20050156351A1 (en) * | 2004-01-20 | 2005-07-21 | Omnova Solutions, Inc. | Apparatus and method for in-mold coating an article by injecting an in-mold coating through the article |
US7279059B2 (en) * | 2004-12-28 | 2007-10-09 | Owens Corning Intellectual Capital, Llc | Polymer/WUCS mat for use in automotive applications |
US7252729B2 (en) * | 2004-12-29 | 2007-08-07 | Owens-Corning Fiberglas Technology Inc. | Polymer/WUCS mat for use in sheet molding compounds |
US8652288B2 (en) * | 2006-08-29 | 2014-02-18 | Ocv Intellectual Capital, Llc | Reinforced acoustical material having high strength, high modulus properties |
US20100143692A1 (en) * | 2008-12-10 | 2010-06-10 | Ryan James P | Carbon and Glass Fiber Reinforced Composition |
US20140221553A1 (en) * | 2013-02-07 | 2014-08-07 | Holland Composites Innovation B.V. | Composite materials and shaped articles |
JP5767415B1 (en) | 2013-08-13 | 2015-08-19 | 帝人株式会社 | Decorative molded product manufacturing method and decorative molded product |
JP6215889B2 (en) * | 2015-10-14 | 2017-10-18 | 株式会社タカギセイコー | Composite molding system |
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GB2051829A (en) * | 1979-06-21 | 1981-01-21 | Gen Tire & Rubber Co | In-mould thermoset coating of moulded foamed articles |
GB2119282A (en) * | 1982-04-26 | 1983-11-16 | Great Lakes Carbon Corp | Coated fiber-reinforced body and method of making |
EP0341977A2 (en) * | 1988-05-10 | 1989-11-15 | E.I. Du Pont De Nemours And Company | Composites from wet formed blends of glass and thermoplastic fibers |
EP0372740A2 (en) * | 1988-12-02 | 1990-06-13 | Ppg Industries, Inc. | Process for coating plastic substrates with powder coating compositions |
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US4081578A (en) * | 1974-06-27 | 1978-03-28 | The General Tire & Rubber Company | In-mold coating composition and method of applying same |
US4189517A (en) * | 1978-11-08 | 1980-02-19 | The General Tire & Rubber Company | Low-shrink in-mold coating |
US4457797A (en) * | 1982-03-08 | 1984-07-03 | E. I. Dupont De Nemours And Company | Process for thermoforming reinforced polymer sheets |
US4716072A (en) * | 1986-12-29 | 1987-12-29 | General Electric Company | Multilayer composite structure for smooth surfaces |
US4737403A (en) * | 1987-04-03 | 1988-04-12 | Ppg Industries, Inc. | Method of coating fiber-reinforced plastic substrates |
US4948661A (en) * | 1987-07-10 | 1990-08-14 | C. H. Masland & Sons | Glossy finish fiber reinforced molded product and processes of construction |
US4781876A (en) * | 1987-07-16 | 1988-11-01 | General Motors Corporation | Method of producing glass fiber mat reinforced plastic panels |
JPH01198314A (en) * | 1988-02-03 | 1989-08-09 | Honda Motor Co Ltd | Method and apparatus for preparing composite molded object |
US5009821A (en) * | 1989-02-23 | 1991-04-23 | Libbey-Owens-Ford Co. | Molding method for eliminating fiber readout |
US4983247A (en) * | 1989-08-07 | 1991-01-08 | General Electric Company | Method for producing resin rich surface layer on composite thermoplastic material |
US5134016A (en) * | 1990-10-31 | 1992-07-28 | E. I. Du Pont De Nemours And Company | Fiber reinforced porous sheets |
-
1992
- 1992-02-21 JP JP5514782A patent/JPH07503912A/en active Pending
- 1992-02-21 ES ES92912089T patent/ES2111069T3/en not_active Expired - Lifetime
- 1992-02-21 AU AU20140/92A patent/AU2014092A/en not_active Abandoned
- 1992-02-21 DE DE1992623806 patent/DE69223806T2/en not_active Expired - Fee Related
- 1992-02-21 CZ CZ942000A patent/CZ9402000A3/en unknown
- 1992-02-21 WO PCT/US1992/001391 patent/WO1993016856A1/en not_active Application Discontinuation
- 1992-02-21 BR BR9207085A patent/BR9207085A/en not_active IP Right Cessation
- 1992-02-21 EP EP19920912089 patent/EP0626901B1/en not_active Expired - Lifetime
- 1992-02-21 CA CA 2130120 patent/CA2130120A1/en not_active Abandoned
-
1996
- 1996-01-24 US US08/590,959 patent/US5632949A/en not_active Expired - Fee Related
Patent Citations (5)
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EP0006308A1 (en) * | 1978-06-08 | 1980-01-09 | Ici Americas Inc. | In-mould coating compositions containing functional group terminated liquid polymers and method of covering surface defects of a moulded thermoplastic article therewith |
GB2051829A (en) * | 1979-06-21 | 1981-01-21 | Gen Tire & Rubber Co | In-mould thermoset coating of moulded foamed articles |
GB2119282A (en) * | 1982-04-26 | 1983-11-16 | Great Lakes Carbon Corp | Coated fiber-reinforced body and method of making |
EP0341977A2 (en) * | 1988-05-10 | 1989-11-15 | E.I. Du Pont De Nemours And Company | Composites from wet formed blends of glass and thermoplastic fibers |
EP0372740A2 (en) * | 1988-12-02 | 1990-06-13 | Ppg Industries, Inc. | Process for coating plastic substrates with powder coating compositions |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0933195A1 (en) * | 1997-12-17 | 1999-08-04 | Freistaat Bayern, vertreten durch Friedrich-Alexander-Universität Erlangen-Nürnberg | Fibre-reinforced synthetic structure |
EP3603924A4 (en) * | 2017-06-22 | 2020-04-29 | Mitsubishi Heavy Industries, Ltd. | Method for producing composite material structure |
Also Published As
Publication number | Publication date |
---|---|
US5632949A (en) | 1997-05-27 |
EP0626901A1 (en) | 1994-12-07 |
CZ9402000A3 (en) | 1994-12-15 |
JPH07503912A (en) | 1995-04-27 |
DE69223806T2 (en) | 1998-07-23 |
AU2014092A (en) | 1993-09-13 |
ES2111069T3 (en) | 1998-03-01 |
CA2130120A1 (en) | 1993-09-02 |
DE69223806D1 (en) | 1998-02-05 |
EP0626901B1 (en) | 1997-12-29 |
BR9207085A (en) | 1995-12-12 |
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