WO1994025528A1 - Composition thermodurcissable moulable par injection, notamment pour carrosserie de vehicules automobiles, procede d'obtention et procede de recyclage - Google Patents
Composition thermodurcissable moulable par injection, notamment pour carrosserie de vehicules automobiles, procede d'obtention et procede de recyclageInfo
- Publication number
- WO1994025528A1 WO1994025528A1 PCT/FR1994/000500 FR9400500W WO9425528A1 WO 1994025528 A1 WO1994025528 A1 WO 1994025528A1 FR 9400500 W FR9400500 W FR 9400500W WO 9425528 A1 WO9425528 A1 WO 9425528A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition according
- fibers
- thermosetting
- mineral fillers
- composition
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 10
- 238000004064 recycling Methods 0.000 title claims description 7
- 238000002347 injection Methods 0.000 title claims description 3
- 239000007924 injection Substances 0.000 title claims description 3
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000012764 mineral filler Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 9
- 239000002956 ash Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 239000012783 reinforcing fiber Substances 0.000 claims description 9
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000004760 aramid Substances 0.000 claims description 4
- 229920006231 aramid fiber Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920001567 vinyl ester resin Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000008247 solid mixture Substances 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 239000004412 Bulk moulding compound Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- 229920000271 Kevlar® Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004761 kevlar Substances 0.000 description 4
- 244000198134 Agave sisalana Species 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002512 anti-withdrawal effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/10—Epoxy resins modified by unsaturated compounds
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
Definitions
- Injection moldable thermosetting composition in particular for bodywork of motor vehicles, process for obtaining and process for recycling.
- the present invention relates to a thermosetting composition which can be used in particular in the manufacture of body parts for motor vehicles, a process for obtaining this composition as well as a process for recycling the parts produced in this composition.
- thermosetting materials of the BMC (Bulk Molding Compound) type comprise, conventionally, approximately 50% of mineral fillers such as chalk or alumina and of the order of 20% of glass fibers, the remainder consisting of a polyester resin. Such a composition leads to a density of around 1.8.
- thermosetting compositions have a number of drawbacks.
- thermosetting composition characterized in that it comprises approximately by weight:
- thermosetting resin - 33% to 43% of a thermosetting resin
- Such a composition therefore comprises much less mineral fillers than known compositions, in particular than BMCs.
- composition according to the invention can comprise approximately 10% of cellulose fibers.
- thermosetting resin can be chosen from polyesters with a mallic, orthophthalic, isophthalic or adipic base, or vinylesters with a urethane or epoxy base.
- the reinforcing fibers may in particular be chosen, at least in part, from glass, carbon or aramid fibers, such as those sold under the brand Kevlar by the company Dupont de Nemours.
- the mineral fillers can on the other hand be chosen at least in part from calcium carbonate and hydrated alumina.
- composition according to the invention can also comprise approximately 15% to 25% by weight of anti-shrinkage additive.
- a composition according to the invention which is particularly advantageous for the production of body parts for motor vehicles comprises by weight, approximately 30% of resin, 20% of an anti-shrinkage additive, 0.5% of catalyst, 10% of fibers. cellulose, 18% mineral fillers, 2% of a release agent and 17.5% of reinforcing fibers with high mechanical resistance.
- These reinforcing fibers can more particularly comprise from 1% to 3% of the total weight of aramid fibers, for example Kevlar.
- the present invention also relates to a process for obtaining a thermosetting composition as described above in which, firstly, on the one hand, the mineral fillers and the solid fibers are mixed separately. on the other hand the other components, liquids, and, in a second step, the solid mixture is impregnated using the liquid mixture.
- the present invention also relates to a process for recycling a part produced in a composition as described above in which said part is burned and the ashes are used as fillers in a new thermosetting composition.
- the density of the compositions according to the invention is of the order of 1.3, so that the parts molded in this composition are considerably lightened compared to the equivalent parts molded in conventional BMCs.
- cellulose fibers which can be of various origins (wood, cotton, sisal %) and of different lengths (a few microns to several millimeters).
- compositions according to the invention does not require maturation (salification), unlike also BMCs.
- Table 1 below gives ranges of percentages by weight of the various components of compositions according to the invention.
- the anti-shrinkage additives, the catalysts, the mineral fillers, the release agents as well as the reinforcing fibers with high mechanical strength indicated here are only by way of non-limiting example, other components already known to possess these properties can be used. The same applies to thermosetting resins.
- Table 2 below provides the physical, mechanical and electrical characteristics of parts molded from four materials with the following compositions:
- compositions a and d comprise 10% of cotton fibers, the composition b, 5% and the composition c, 15%.
- composition d comprises 2% of Kevlar fibers.
- the cellulose fibers make it possible to lower the density significantly compared to conventional BMCs.
- the mechanical performance and particularly the breaking stress at bending are staggered according to the formulations between 120 and 212 MPa, while the conventional polyester BMC loaded with 18% glass fibers reaches only 80 - 100 MPa.
- the impact resistances are, according to the formulas, from 18 to 32 kJ / m2 while the conventional polyester BMC is between 15 and 20 kJ / m2.
- the flexural modules of between 11,000 and 13,000 MPa are directly linked to the cracking coefficient of the different resins used, which explains why the performances are relatively less improved compared to those of conventional BMCs.
- the impact strengths can be improved by a higher rate of glass fibers, it being understood that each additional percent increases the density by 0.02.
- the formula a with 17.5% of glass fibers has a density of 1.33 against 1.383 for the same formula a with 20% of glass fibers.
- the materials according to the invention can be obtained in a series of steps using two mixers.
- a first ribbon mixer allows a homogeneous mixture of the different mineral fillers, cellulose fibers and glass fibers.
- the output of this mixer is directly connected to the second mixer.
- This second Z-arm mixer is used initially for mixing liquid elements (resins, catalysts, dyes, etc.). It is then used for the final operation of impregnating the mixture with the solid elements using the liquid mixture.
- the first ribbon mixer has a capacity of 1,200 liters and is loaded with 300 kg of solids. These materials are kneaded there for one minute to one and a half minutes at 42 rpm.
- the second mixer with a Z-arm, also has a capacity of 1,200 liters and also operates at 42 rpm.
- the mixing of the liquid components lasts about 10 min and the impregnation of the solid components from 4 to 6 min depending on the percentage of glass fibers.
- the recycling of molded parts in such a material can be carried out using an oven with a power of the order of 5 kw, a hammer mill with a power of about 2.2 kw and a vibratory screen having for example a diameter of the order of 650 mm, a mesh of 2 mm and a power of about 2.2 kw.
- the oven allows the combustion of the parts to be recycled, the hammer crusher to break the blocks of ash, and the vibrating sieve to separate in these crushed ashes the glass fibers of the chalk.
- the material consumes between 500 and 580 degrees C because it is very little loaded with non-combustible material (about 30%) and behaves on combustion like charcoal.
- the combustion can be carried out in a coal-fired thermal power plant.
- the ashes can then be recovered for the development of new composites or be stored on crassier or heap for road works (embankments, motorways ). These ashes, being composed of pulverized chalk and micronized glass, have no harmful effects on the environment and particularly on the water table.
- the flue gases include water vapor, carbon dioxide and carbon monoxide.
- the carbon dioxide / carbon monoxide ratio is 95/5. It is important to note the absence of sulfur dioxide and toxic gases (chlorine, bromine, ).
- the ashes can, after grinding, be directly reused in formulations of composite materials as mechanical or other reinforcing fillers.
- the powdered ash composed of 95% calcium carbonate and 5% micronized glass is recycled as mineral fillers in composite materials to lower the cost price.
- the ground glass fibers separated at 100% serve for mechanical reinforcement of formulations, of composition according to the invention or others.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94915198A EP0698060A1 (fr) | 1993-05-04 | 1994-05-02 | Composition thermodurcissable moulable par injection, notamment pour carrosserie de vehicules automobiles, procede d'obtention et procede de recyclage |
US08/537,824 US5767177A (en) | 1993-05-04 | 1994-05-02 | Injection mouldable thermosetting composition especially for motor vehicle bodies, method of production and method or recycling |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR93/05293 | 1993-05-04 | ||
FR9305293A FR2704863B1 (fr) | 1993-05-04 | 1993-05-04 | Composition thermodurcissable, notamment pour carrosserie de vehicules automobiles, procede d'obtention et procede de recyclage. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994025528A1 true WO1994025528A1 (fr) | 1994-11-10 |
Family
ID=9446723
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1994/000500 WO1994025528A1 (fr) | 1993-05-04 | 1994-05-02 | Composition thermodurcissable moulable par injection, notamment pour carrosserie de vehicules automobiles, procede d'obtention et procede de recyclage |
Country Status (4)
Country | Link |
---|---|
US (1) | US5767177A (fr) |
EP (1) | EP0698060A1 (fr) |
FR (1) | FR2704863B1 (fr) |
WO (1) | WO1994025528A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2306909A (en) * | 1995-11-09 | 1997-05-14 | Panel Holdings Ltd | Moulded articles from a polyurethane matrix and fillers |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5973035A (en) | 1997-10-31 | 1999-10-26 | Xyleco, Inc. | Cellulosic fiber composites |
US20030187102A1 (en) | 1997-09-02 | 2003-10-02 | Marshall Medoff | Compositions and composites of cellulosic and lignocellulosic materials and resins, and methods of making the same |
US6448307B1 (en) | 1997-09-02 | 2002-09-10 | Xyleco, Inc. | Compositions of texturized fibrous materials |
US6217805B1 (en) | 1999-01-08 | 2001-04-17 | Lear Corporation | Fiber choppers for molding processes |
US20030220036A1 (en) * | 2000-12-20 | 2003-11-27 | Lee Robert A. | Laminates and coated materials comprising hydroxy-phenoxyether polymers |
US7435483B2 (en) * | 2001-04-04 | 2008-10-14 | Advanced Plastics Technologies Luxembourg S.A. | Process for coating paper, paperboard, and molded fiber with a water-dispersible polyester polymer |
US6758996B2 (en) | 2001-07-13 | 2004-07-06 | Kadant Composites Inc. | Cellulose-reinforced thermoplastic composite and methods of making same |
US7313865B2 (en) * | 2003-01-28 | 2008-01-01 | Zephyros, Inc. | Process of forming a baffling, sealing or reinforcement member with thermoset carrier member |
SG149671A1 (en) * | 2004-06-11 | 2009-02-27 | Gpac Technology S Pte Ltd | Pallet and method for manufacturing the same |
DK2564931T3 (da) | 2005-03-24 | 2014-08-25 | Xyleco Inc | Fremgangsmåder til fremstilling af fibrøse materialer |
US7708214B2 (en) | 2005-08-24 | 2010-05-04 | Xyleco, Inc. | Fibrous materials and composites |
US20150328347A1 (en) | 2005-03-24 | 2015-11-19 | Xyleco, Inc. | Fibrous materials and composites |
JP6454957B2 (ja) * | 2013-09-27 | 2019-01-23 | Dic株式会社 | ラジカル硬化性樹脂組成物及び土木建築材料 |
US20190224929A1 (en) * | 2016-06-23 | 2019-07-25 | Fpinnovations | Wood pulp fiber- or cellulose filament-reinforced bulk molding compounds, composites, compositions and methods for preparation thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE662820A (fr) * | 1964-04-21 | 1965-08-17 | ||
DE2256968A1 (de) * | 1971-11-22 | 1973-05-24 | Richard A Wallace | Verbundwerkstoff und herstellungsverfahren |
FR2334716A1 (fr) * | 1975-12-08 | 1977-07-08 | Budd Co | Maturation de compositions de polyester pour reglage de l'indice de viscosite |
GB2103639A (en) * | 1981-08-03 | 1983-02-23 | Scott Bader Co | Reinforced polyester moulding compositions |
EP0498060A2 (fr) * | 1991-02-02 | 1992-08-12 | Hüls Aktiengesellschaft | Masses à mouler à base de polyesters insaturés contenant des fibres naturelles et objets moulés obtenus à partir de celles-ci |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3991005A (en) * | 1971-11-22 | 1976-11-09 | Wallace Richard A | Structural material and method |
-
1993
- 1993-05-04 FR FR9305293A patent/FR2704863B1/fr not_active Expired - Fee Related
-
1994
- 1994-05-02 US US08/537,824 patent/US5767177A/en not_active Expired - Fee Related
- 1994-05-02 EP EP94915198A patent/EP0698060A1/fr not_active Withdrawn
- 1994-05-02 WO PCT/FR1994/000500 patent/WO1994025528A1/fr not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE662820A (fr) * | 1964-04-21 | 1965-08-17 | ||
DE2256968A1 (de) * | 1971-11-22 | 1973-05-24 | Richard A Wallace | Verbundwerkstoff und herstellungsverfahren |
FR2334716A1 (fr) * | 1975-12-08 | 1977-07-08 | Budd Co | Maturation de compositions de polyester pour reglage de l'indice de viscosite |
GB2103639A (en) * | 1981-08-03 | 1983-02-23 | Scott Bader Co | Reinforced polyester moulding compositions |
EP0498060A2 (fr) * | 1991-02-02 | 1992-08-12 | Hüls Aktiengesellschaft | Masses à mouler à base de polyesters insaturés contenant des fibres naturelles et objets moulés obtenus à partir de celles-ci |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2306909A (en) * | 1995-11-09 | 1997-05-14 | Panel Holdings Ltd | Moulded articles from a polyurethane matrix and fillers |
GB2306909B (en) * | 1995-11-09 | 2000-03-29 | Panel Holdings Ltd | Moulded articles their production and use |
Also Published As
Publication number | Publication date |
---|---|
EP0698060A1 (fr) | 1996-02-28 |
US5767177A (en) | 1998-06-16 |
FR2704863B1 (fr) | 1995-06-23 |
FR2704863A1 (fr) | 1994-11-10 |
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