EP0304368A1 - Compositions de nappes thermoplastiques déposées par voie humide - Google Patents

Compositions de nappes thermoplastiques déposées par voie humide Download PDF

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Publication number
EP0304368A1
EP0304368A1 EP88402035A EP88402035A EP0304368A1 EP 0304368 A1 EP0304368 A1 EP 0304368A1 EP 88402035 A EP88402035 A EP 88402035A EP 88402035 A EP88402035 A EP 88402035A EP 0304368 A1 EP0304368 A1 EP 0304368A1
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Prior art keywords
component
parts
fibers
composition according
composition
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EP88402035A
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German (de)
English (en)
Inventor
Pierre Fredenucci
Christophe Chartier
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Publication of EP0304368A1 publication Critical patent/EP0304368A1/fr
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
    • D21J1/00—Fibreboard
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/24—Polyesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments

Definitions

  • the invention relates to paper compositions intended especially for forming a reinforced thermoplastic web which can be hot-stamped into a finished product.
  • compositions intended for forming a web of this type mainly contain fibers for reinforcing the product during manufacture (such as cellulose or the like), fibers for reinforcing the finished product (such as glass fibers or the like), a thermoplastic resin under particulate form, optionally a binder (such as latices in aqueous suspension or the like).
  • the compositions can also contain universal fibers, essentially to reinforce the finished product, by replacing at a lower cost a part of the reinforcing fibers.
  • the process for the manufacture of the web from the paper composition is a conventional paper-making process such as the one described in the above-mentioned documents, with passage through a paper machine, for example a Fourdrinier machine with a flat table or an inclined wire.
  • the wet process comprises forming an aqueous slurry comprising polymer particles, fibers such as glass fibers which provide reinforcement in the final products, and process aids.
  • the slurry is then laid down in a thin layer on a moving mesh through which the water drains, optionally under negative pressure, to leave a wet web of particles and fibers.
  • the web is then carried through a drying means such as an infra red oven or a hot air jet.
  • the dried, so called wet laid web is then subjected to densification by hot pressing or moulding to form a (glass) fiber reinforced polymer product.
  • the requirements for a good composition are inter alia : . to lead to the formulation of a homogeneous and regular web. . to authorize the highest possible producing speed. . to provide the web with a strength sufficient to permit its drying, its handleability and its transformation.
  • the requirements for a good composition, as regards transformation of the web thus obtained are : . a good capacity of the web to be heated at a temperature higher than the melting temperature of the thermoplastic resin. . the highest possible mouldability.
  • compositions meeting this criterion are : . to permit a surface appearance as regular as possible . to have a thermical stability adequate for the industrial lines of painting . to have the best possible dimensional stability under any weather conditions.
  • the object of the invention is to propose paper compositions meeting all the above-cited requirements and more especially intended for forming a finished product whose appearance satisfies relatively high quality criteria, for example a CLASS A surface finish for visible parts of automobile bodywork.
  • a wet laid fibrous web composition suitable for moulding into a reinforced thermoplastic product comprising fibers for reinforcing the composition during its manufacture, fibers for reinforcing the moulded product, and a thermoplastic resin, said composition comprising the following in parts by dry weight (based on 100 parts of the first, second and third components combined):
  • the proportions of the first, second and third components may be varied independently within quite wide limits, depending on the balance of properties (mechanical strength of final product, handleability of the wet laid web composition in wet and dry (fused) state, mouldability of composition, water absorbance of moulded product).
  • the invention provides a method for producing a moulded product from such a fibrous web composition which comprises pre-heating the web to a temperature which is lower than the melting or degradation temperature of the first component, but greater than the melting temperature of the third component, to fuse the third component but retain the reinforcing effect of the first component, and, in a press, moulding the heated web under pressure at a temperature which is lower than the melting temperature of the third component, to form the desired moulded product.
  • the preheat temperature is at least 30 degrees C greater than the melting temperature of the third component.
  • the first component serves to provide strength to the fused web during the handling associated with the pressing stage during transfer from the heating zone to the press, which may also be heated to provide improved control over cooling the product.
  • the fibers for reinforcing the product during manufacture are the mineral or organic fibers with a physical structure identical or close to that of cellulose, i.e. having an irregular shape with a high specific area. Thus, they contribute to the cohesion of the wet and dry web during passage through the paper machine and then during handling and cutting of the dry sheet, and help to prevent the thermoplastic material from shrinking during drying.
  • the fibers for reinforcing the composition during its manufacture preferably have a melting or degradation temperature at least 20 degrees C greater than the temperature of transformation of the polyester fibres used (for example above 310°C if the thermoplastic material is PETP).
  • the glass fibers owing to their structure, also prevent the flowing, i.e. the disorganization of the web and the running of the resin during preheating of a format or a pile of formats from the web, prior to moulding or transforming into a rigid densified plate.
  • transformation means the technique by which the web containing the first, second and third fibrous components is converted into the finished thermoplastic product of improved mechanical properties (derived from the second component).
  • the web is subjected to an elevated temperature such that the polyester third component melts.
  • the first component shows its value : without the presence of the first component the molten thermoplastic polyester would run and be un-handleable.
  • the second component In the presence of the second component the web maintains its integrity and can be transported to a moulding stage where it is subjected to pressure and cooled, so that the polyester cools into a continuous matrix in which the reinforcing second component fibers are homogeneously dispersed.
  • the moulding can be into a flat sheet (otherwise known as a plaque or blank) which can be used per se or moulded into a more complex shaped article; or the moulding can be directly into a three dimensional shaped article.
  • the fibrous first and second components provide different reinforcement to the web or final product.
  • the first component serves to hold the second and third component fibers together when in the wet or unfused dry state, and to hold the second component fibers and matrix together when the polyester is in the fused state.
  • the first component preferably has a fibrillated structure which gives improved entanglement capability. It is preferred that no binder is used in performance of the wet process to produce the web.
  • the second component fibers are intended to provide reinforcement in the final moulded product and so have a high modulus of elasticity such as is possessed by glass fibres.
  • the web With a cellulose content less than 3% of the fibrous combination, the web has not a sufficient cohesion for its manufacture and its preheating.
  • the composition has a reduced mouldability, and the moulded product becomes wet-sensitive and hence loses dimensional stability.
  • the fibers for reinforcing the finished product are advantageously glass fibers with a length of less than 50 mm and even preferably less than 25 mm.
  • the glass fibers are from 6 to 25 mm long.
  • they are from 9 to 15, more preferably 10 to 12 microns in diameter.
  • Other suitable fibers, above or in combination, and also dispersed in unitary conditions are carbon fibers, metal or metallized fibers, mineral fibers (rock wool, ceramic, boron, etc.) or organic fibers (carbon, polyaramide, polycarbonate, etc.).
  • the proportion of second component present in the composition of the invention can be varied in dependence on the balance of mouldability and mechanical strength required of the final product.
  • a high concentration gives good mechanical strength but can impair mouldability, whereas a low concentration gives good mouldability but a diminished mechanical strength.
  • the composition comprises from 15 to 40 parts by weight of second component fibers (based on 100 parts of first, second and third components) more preferably from 18 to 27 parts by weight and most preferably from 21 to 26 parts by weight.
  • thermoplastic polyester i.e. the third component
  • the thermoplastic polyester is advantageously either a polyethylene terephthalate (PETP) although other polyalkylene terephthalates and other fiber-forming polyesters may be used.
  • PETP is particularly suitable : its melting point of 240-250°C enables it to withstand the temperatures in the paintshops of automobile production lines, which approach 140°C-160°C.
  • the polyester in the paper composition is in the form of microfibers or fibers, and preferably fibers 3 to 6 mm long. It has been found noticeably more advantageous to use thermoplastic fibers rather than thermoplastic powders, because the repartition of the resin in the web is more regular. Another advantage is that the draining speed of the suspension during manufacture of the web or the wire, is quite higher, which permits, when compared to a composition with powder, to produce more rapidly and/or to dilute more in order to better disperse the reinforcing fibers.
  • the heated web although having with fibers a density less than it would have with powders, and hence a greater "content" of air, exhibits a shorter preheating time under the press, which is indeed surprising when one considers that the air present in the product is a poor conductor of heat.
  • compositions of the present invention may therefore be compared with advantage with the compositions taught in WO 87/04476 (Battelle Memorial Institute), which prior art compositions have a heat fusible polymeric component present in the form of particles, rather than fibers.
  • the amount of polyester in the composition depends on the amounts of the first and second components of course, but is preferably in the range from 45 to 85 parts by weight, more preferably from 58 to 79 and most preferably from 65 to 75 parts by weight (based on 100 parts of first, second and third components combined).
  • the fibers of the first component have a melting or degradation temperature greater than that of the third component, in order to provide strength to the composition in the preheated state immediately prior to final moulding or hot pressing.
  • the first component has a melting or degradation temperature at least 50 degrees C and more preferably at least 65 degrees C greater than that of the third component.
  • composition of the invention may also contain fillers.
  • the fillers are all the fillers conventionally used in the art, especially carbonates, talc, etc.
  • the filler is present, if at all, in an amount up to 45 parts by weight (based on 100 parts of first, second and third components), for example from 20 to 45 parts by weight.
  • the composition can also contain the additives or aids necessary to the manufacture, the transformation of the web or utilization of the moulded products.
  • additives or aids necessary to the manufacture, the transformation of the web or utilization of the moulded products include the following may be mentioned : colorants, antioxidants, lubricants, mold release or slip agents, peroxides, antistatic agents, nucleating agents, plasticizers, pigments, flocculants, retention agents, dispersants, flame retardants, water repellants, coupling agents, adhesion primers, UV inhibitors, etc.
  • IMC in-mold coating
  • Table I shows the passage characteristics of tests 1 to 23 on a pilot paper machine.
  • the first column indicates the test number.
  • the second column indicates the weight of the sheet in g/m2.
  • the third column indicates the position of the water line by reference to the corresponding chain line, this number being, for a same dilution, all the higher as the composition drains less.
  • the fourth column indicates the dilution, namely the rate at which water has to be supplied in order to keep the water line in its given position.
  • the fifth and sixth columns indicate the amount of dry matter present at the head of the machine and in the white water respectively.
  • the seventh column gives the wet porosity on entering the dry end, measured in ml/min on a Bendsten porosimeter.
  • the eighth column gives the dryness of the sheet on leaving the wire, before drying.
  • Table II refers to the conversion of the sheets by preheating between the platens of a hot press at 300°C.
  • the first column indicates the test number.
  • the next four columns relate to the conditions of the preheating test and respectively indicate the number of piles, the total number of formats, the size of the format (either rectangular and 15 x 11 cm2 or round and 18 cm in diameter) and their total weight.
  • the sixth column indicates the calculated pressure on the piles of heated formats.
  • the seventh column shows the preheating time required to reach 290°C at the core of the formats.
  • Table III relates to a plate molding tests. Two types of mold were used : the mold shown as no.1 in the second column is a straight-edged plate mold with a circular rib on the bottom, and mold no. 2 is an ordinary hollow plate mold.
  • the third column shows information on the stack formats used to produce the plates.
  • the fourth column relates to the visual appearance of the surface of the molding (homogeneity and evenness).
  • the fifth column indicates the thickness of the plate, the sixth its density and the seventh the percentage of ash.
  • the last three columns respectively indicate the tensile and flexural stresses and flexural modulus.
  • Two values are indicated for the compositions with fillers, these corresponding respectively to the percentage of ash for the fillers and for the glass fibers.
  • Tests 1 to 10 relate to compositions without fillers and tests 11 to 20 relate to compositions with fillers.
  • compositions with cellulose 1.1. Compositions with cellulose
  • Tests 1 to 6 involve compositions with cellulose, containing the following in parts in dry weight : Cellulose fibers 10 Glass fibers 21.5 PETP 68.5
  • the glass fibers are R18DX9 fibers marketed by OWENS CORNING FIBERGLAS EUROPE, with a length of 6 mm and a diameter of 11 micrometers.
  • the aqueous suspension is prepared in a chest in the following manner :
  • the cellulose fiber refined beforehand to between 15 and 65 degress SR, particularly about 50, is introduced at a concentration of the order of 10 to 50 g/l, particularly about 30 g/l, with agitation ; - the polyester fiber in the commercial form is added to the cellulose ; - this is followed by the dispersant for the glass fiber, namely, for the fibers used, a cationic dispersant based on fatty acids - Cartaspers DS1 (registered trademark of SANDOZ) - at a rate of 10% of the commercial product, relative to the dry glass fiber ; and - finally, the glass fiber is added last in the commercial form.
  • the dispersant for the glass fiber namely, for the fibers used, a cationic dispersant based on fatty acids - Cartaspers DS1 (registered trademark of SANDOZ) - at a rate of 10% of the commercial product, relative to the dry glass fiber ; and - finally, the glass fiber is added last in the commercial form.
  • the PETP is the T 100 polyester from RHONE-POULENC, in the form of 6 mm fibers of 3.3. dtex.
  • the PETP is the T 100 polyester from RHONE-POULENC, in the form of 3 mm fibers of 17 dtex.
  • the PETP is the GRILON NV2 polyester from GRILENE, in the form of 6 mm fibers of 3.3 dtex.
  • the PETP is the T 100 polyester from RHONE-POULENC, in the form of powder with a particle size of less than 300 micrometers.
  • Comparison with test no. 1 in Table I shows the very distinct advantage of the composition with fibers as far as draining is concerned.
  • the porosity is similar, however, which is surprising.
  • the PETP is the 6438 polyester from Eastman Kodak, with a mean particle size of 200 micrometers. This test confirms the preceding one.
  • Table I shows that the draining is very slow
  • Table II shows that the preheating time is very long
  • Table III shows that the percentage of ash is high, indicating that the PETP in powder form has a low retention, which may justify the relatively inferior characteristics.
  • the poor appearance of the molded plate should be noted, this being related to the very long preheating time which results in surface degradation of the material.
  • the PTEP is a polyester supplied by ENKA, ground to a particle size of less than 300 micrometers.
  • ENKA ENKA
  • thermoplastic fibers instead of powders allows a better capacity to be produced in machine, a higher productivity and a transformation made much easier.
  • compositions without cellulose for comparison
  • This type of composition leads to a product which is impossible to draw satisfactorily through an industrial paper machine with a wet and a dry end, due to the lack of cohesion and the high shrinkage during drying.
  • Table II indicates very significant flow : the material flows and makes it necessary to fold the assembly into a ball ; the material cools. The process is not industrial.
  • test no.7 is carried out again by adding as fibers with a high specific area, a synthetic polyolefin pulp.
  • Glass fibers (as in test 7) 22.4 parts PETP (as in test 7) 71.2 parts PULPEX EA polyethylene pulp marketed by HERCULES 6.4 parts.
  • Table II indicates that the preheating had to be stopped before reaching 290°C because of very significant flow.
  • the PULPEX E A used had fiber length from 0.2 to 1.3 mm and diameter from 10 to 20 microns.
  • composition is the same as in test 8 but the preheating conditions are altered in an attempt to overcome the problem encountered in the previous test.
  • compositions with cellulose 1.2.2. Compositions with cellulose
  • the composition of test 10 contains cellulose and the same T 900 PETP polymer as in test 7.
  • the composition is as follows : Cellulose 10 parts Glass fibers 21.5 parts PETP 68.5 parts
  • the slightly branched T 900 polymer is an inferior grade of polymer to the linear T 100 in terms of the mechanical strengths, which largely explains the drop in the characteristics compared with test no. 1.
  • compositions with PETP fibers 2.1. Compositions with PETP fibers
  • the filler used is a Millicarb carbonate marketed by OMYA.
  • the mineral filler is introduced into the refined cellulose before the polyester.
  • a customary retention agent has to be added at the head of the machine in order to ensure a good retention of the said filler. Good results were obtained with a high-molecular poly-acryamide at a rate of 0.2% relative to the dry materials.
  • a mixture of this type is then diluted to the desired concentration to enable it to pass satisfactorily through the paper machine.
  • the fibers are the T 100 PETP from Rhone-Poulenc, 6 mm, 17 dtex.
  • the final appearance of the plates shows fewer wrinkles than for a composition without a filler.
  • the fibers are the T 100 PETP from Rhone-Poulenc, 6 mm, 3.3 dtex.
  • the fibers are a PTEP from MONTEFIBRE, with a length of 6 mm.
  • the reduction in wrinkles is less substantial than with the PTEP from Rhöne-Poulenc and the percentage of ash in the fillers indicates a problem of filler retention.
  • the fibers are DACRON PETP fibers from DUPONT DE NEMOURS, D157N, 6 mm, 7 dtex.
  • the powder is the T 100 PETP from Rhône-Poulenc, with a particle size of less than 300 micrometers.
  • test shows, with the fibers, a surface appearance improved in comparison to test no. 4, but with a noticeable reduction of the draining and a preheating time increased in comparison to test no. 11.
  • the powder is the 64-38 PTEP from Kodak, with a mean particle size of 200 micrometers.
  • the wrinkles are analogous to those obtained with the compositions with Rhône-Poulenc fibers, but there are more dull specks.
  • PETP being in the form of T 100 PETP fibers from Rhône-Poulenc, 3mm, 17 dtex.
  • the filler is OMYA Millicarb carbonate with a mean particle size of 1 to 2 micrometers.
  • the filler is B038 carbonate from Blanc Minéraux de Paris, with a particle size of 10 to 12 micrometers.
  • the filler is no. 2 talc (hydrated magnesium silicate) from Talcs de Luzenac, with a means particle size of 12 micrometers.
  • the surface appearance is still better than in the case of the compositions with carbonates.
  • the fibers for reinforcing the finished product are essential, so it is of course preferable to reduce the proportion of reinforcing fibers necessary for manufacture.
  • compositions without mineral fillers for the purpose of evaluating the minimum proportion of cellulose fibers which has to be introduced in order to permit satisfactory production on a conventional paper machine or during the handling operations prior to molding, without detracting from the moldability.
  • T 100 PETP polyester from Rhône-Poulenc in the form of 6 mm fibers of 17 dtex, and R18DX9 glass fibers marketed by OWENS CORNING FIBREGLASS EUROPE, 6 mm, 11 micrometers.
  • the composition with 5 parts of cellulose is found to have a very distinct advantage over the composition with 2 parts.
  • the latter gives a sheet with very weak wet and dry cohesion and results in very significant flow of the thermoplastic material during preheating. This significant flow and the poor cohesion of the molten material make it impossible to densify it into a rigid sheet or to manipulate this material for placing it in the stamping mold. This type of composition is thus not industrial.
  • composition with 5 parts of cellulose permits correct passage through the paper machine and is sufficiently strong to allow handling, cutting of the dry sheet and preheating without the material flowing.
  • the moldability values collated in Table III represent the distance, in degrees, travelled by the material in a circular direction.
  • the attached diagram shows the plate 1 of which one edge 2 can extend circumferentially, during molding, to form an ear 3, the length of which is measured by a graduated scale 4 on the mold.
  • compositions with cellulose fiber concentration less than about 3 parts by weight generally have inadequate handling strength during preheating prior to hot pressing.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP88402035A 1987-08-04 1988-08-04 Compositions de nappes thermoplastiques déposées par voie humide Withdrawn EP0304368A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8711067 1987-08-04
FR8711067A FR2619117A1 (fr) 1987-08-04 1987-08-04 Composition papetiere notamment pour feuille thermoplastique renforcee estampable

Publications (1)

Publication Number Publication Date
EP0304368A1 true EP0304368A1 (fr) 1989-02-22

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EP88402035A Withdrawn EP0304368A1 (fr) 1987-08-04 1988-08-04 Compositions de nappes thermoplastiques déposées par voie humide

Country Status (7)

Country Link
EP (1) EP0304368A1 (fr)
JP (1) JPH03501276A (fr)
KR (1) KR890701843A (fr)
AU (1) AU2260988A (fr)
BR (1) BR8807638A (fr)
FR (1) FR2619117A1 (fr)
WO (1) WO1989001075A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2403223A (en) * 2003-06-27 2004-12-29 Excel Ind Ltd Composite material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01318045A (ja) * 1988-05-10 1989-12-22 E I Du Pont De Nemours & Co ガラス繊維と熱可塑性繊維との湿式成形混合物よりの複合材料

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB572962A (en) * 1942-05-25 1945-10-31 Sylvania Ind Corp Paper products and methods of making the same
GB1200342A (en) * 1967-06-02 1970-07-29 Ici Ltd Reinforcing thermoplastic materials
FR2346520A1 (fr) * 1976-03-30 1977-10-28 Ici Ltd Recouvrement de mur ou de plafond du type en feuille
GB2070092A (en) * 1978-08-21 1981-09-03 Grace W R & Co Process for producing a web useful as a battery separator
EP0039292A1 (fr) * 1980-04-30 1981-11-04 Arjomari-Prioux S.A. Matériau en feuille transformable, par moulage, estampage ou thermoformage en un produit fini, comportant des fibres de renforcement, une résine thermoplastique en poudre, et procédé de préparation dudit matériau
FR2507123A1 (fr) * 1981-06-04 1982-12-10 Arjomari Prioux Semi-produit composite en feuille constitue d'un composant thermoplastique et d'un renfort en polyaramide, son procede de preparation, et les produits finis correspondants obtenus a chaud
EP0113279A1 (fr) * 1982-12-30 1984-07-11 Société Chimique des Charbonnages Matériaux stratifiés présentant une couche de finition améliorée
EP0151448A1 (fr) * 1984-01-27 1985-08-14 Kureha Chemical Industry Co., Ltd. Procédé de fabrication de films électro-conducteurs
WO1987004476A1 (fr) * 1986-01-17 1987-07-30 Battelle Memorial Institute Composites non-tisses formes par voie humide, renforces par des fibres et contenant une pulpe stabilisatrice

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB572962A (en) * 1942-05-25 1945-10-31 Sylvania Ind Corp Paper products and methods of making the same
GB1200342A (en) * 1967-06-02 1970-07-29 Ici Ltd Reinforcing thermoplastic materials
FR2346520A1 (fr) * 1976-03-30 1977-10-28 Ici Ltd Recouvrement de mur ou de plafond du type en feuille
GB2070092A (en) * 1978-08-21 1981-09-03 Grace W R & Co Process for producing a web useful as a battery separator
EP0039292A1 (fr) * 1980-04-30 1981-11-04 Arjomari-Prioux S.A. Matériau en feuille transformable, par moulage, estampage ou thermoformage en un produit fini, comportant des fibres de renforcement, une résine thermoplastique en poudre, et procédé de préparation dudit matériau
FR2507123A1 (fr) * 1981-06-04 1982-12-10 Arjomari Prioux Semi-produit composite en feuille constitue d'un composant thermoplastique et d'un renfort en polyaramide, son procede de preparation, et les produits finis correspondants obtenus a chaud
EP0113279A1 (fr) * 1982-12-30 1984-07-11 Société Chimique des Charbonnages Matériaux stratifiés présentant une couche de finition améliorée
EP0151448A1 (fr) * 1984-01-27 1985-08-14 Kureha Chemical Industry Co., Ltd. Procédé de fabrication de films électro-conducteurs
WO1987004476A1 (fr) * 1986-01-17 1987-07-30 Battelle Memorial Institute Composites non-tisses formes par voie humide, renforces par des fibres et contenant une pulpe stabilisatrice

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ABSTRACT BULLETIN, vol. 58, no. 4, 4th October 1987, page 563, abstract no. 5163, Appleton, WI, US; & JP-A-62 079 822 (JAPAN INORGANIC FIBER INDUSTRY CO., LTD) 13-04-1987 *
EUROPEAN PLASTICS NEWS, vol. 3, nos. 7/8, July/August 1976, pages 25-27; "Thermoplastic polyesters- glass reinforced PBT leads the way" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2403223A (en) * 2003-06-27 2004-12-29 Excel Ind Ltd Composite material
WO2005000947A1 (fr) * 2003-06-27 2005-01-06 Excel Industries Limited Materiau composite

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KR890701843A (ko) 1989-12-21
AU2260988A (en) 1989-03-01
JPH03501276A (ja) 1991-03-22
BR8807638A (pt) 1990-08-07
WO1989001075A1 (fr) 1989-02-09
FR2619117A1 (fr) 1989-02-10

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