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WO1994025272A1 - Articles en pvc thermoplastique renforce de dimensions stables - Google Patents

Articles en pvc thermoplastique renforce de dimensions stables Download PDF

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Publication number
WO1994025272A1
WO1994025272A1 PCT/US1994/004679 US9404679W WO9425272A1 WO 1994025272 A1 WO1994025272 A1 WO 1994025272A1 US 9404679 W US9404679 W US 9404679W WO 9425272 A1 WO9425272 A1 WO 9425272A1
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WO
WIPO (PCT)
Prior art keywords
article
composite
structural component
structural
plasticizer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1994/004679
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English (en)
Inventor
Bryan Michael Kazmer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Geon Co
Original Assignee
Geon Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Geon Co filed Critical Geon Co
Priority to BR9406364A priority Critical patent/BR9406364A/pt
Priority to AU67770/94A priority patent/AU6777094A/en
Priority to JP6524538A priority patent/JPH08509673A/ja
Priority to KR1019950704916A priority patent/KR960702384A/ko
Priority to EP94915929A priority patent/EP0696963A1/fr
Publication of WO1994025272A1 publication Critical patent/WO1994025272A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
    • B29C70/021—Combinations of fibrous reinforcement and non-fibrous material
    • B29C70/023—Combinations of fibrous reinforcement and non-fibrous material with reinforcing inserts
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of 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
    • C08K5/00—Use of organic ingredients
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers

Definitions

  • This invention relates to composite articles containing flexible fiber reinforced polyvinyl chloride.
  • European patent publication 411 429 published 2-6-91 discloses articles made from high molecular weight polyvinyl chloride, plasticizer, and reinforcement material.
  • the reinforcement material is selected from particulate or fibrous materials.
  • the polyvinyl chloride has a molecular weight in terms of inherent viscosity above 1.0 preferably 1.4 to 1.7. This material is designed to sustain low continuous load and exhibit little or no deflection at high temperatures. Particulate reinforcement is not distinguished from fiber reinforcement.
  • U.S. patent no. 3,892,692 discloses ethylene vinyl chloride copolymers which are plasticized and exhibit improved plasticizer permanence.
  • the copolymers contain a modulus index of less than 3000 psi as compared with rigid polyvinyl chloride having a modulus of 300,000 psi.
  • Any type of reinforcing fillers can be used among those suggested are clay, iron oxide, calcium carbonate, asbestos, glass, rayon, and mineral wool. This patent does not acknowledge that non-fibrous reinforcement behaves differently with respect to dimensional stability when combined in a plasticized, flexible matrix, as compared to fibrous reinforcement.
  • Plasticized polyvinyl chloride has been exploited as a useful tough, weatherable material.
  • US-A-3 084 078 is a general disclosure of phthalate ester, a widely used plasticizer.
  • US-A-2 535 643 discloses a class of plasticizers and any usual commercial PVC (see column 3, lines 20-22).
  • US-A-3 796 681 is directed to plastisols.
  • EP-A-0 057 470 broadly shows non-reinforced plasticized PVC.
  • the fiber reinforcing of rigid thermoplastics has been commercially exploited in structural uses to provide for rigidity (modulus enhancement) beyond that obtainable from the rigid thermoplastic matrix alone.
  • Chopped glass fibers having a diameter from about 10 microns to about 25 microns have been commercially developed specifically for this purpose.
  • the addition of glass fibers to a rigid thermoplastic matrix resin reduces the coefficient of linear thermal expansion (CLTE) of the composite.
  • CLTE coefficient of linear thermal expansion
  • the high tensile or flexural modulus is not needed, however due to poor dimensional stability, the designer often is of the belief that high modulus is needed to prevent distortions in the article.
  • the present invention is contrasted with conventional approaches suggesting high structural strength.
  • the composites of the present invention contain a non- structural component which has low modulus and strength however, this component possesses an improved degree of dimensional stability, thereby avoiding the build-up of load stress under changing environmental conditions of exterior applications.
  • the high dimensional stability of the non-structural component in this invention, over a broad temperature range, is sufficient to enable close tolerance fit with the structural component without distortion of the non-structural component.
  • the structural component (A) is selected from the group consisting of metal sheet, shaped metal articles, rigid thermoplastic, and rigid thermoset articles.
  • the composite optionally and preferably further comprises an appearance (C) layer overlying (A) on the surface not contacting (B).
  • the appearance layer (C) can completely surround (A) or cover only the show side with a small portion extending around the edge of the show side so as to provide a area for trimming (C) which is not seen.
  • (C) comprises a thermoplastic compound such as non-reinforced, pigmented plasticized polyvinyl halide composition, decorative paint and the like.
  • the structural component (B) is generally selected from the group consisting of a rigid molded, stamped or shaped metal article such as a steel, aluminum or thermoset polymer article, a metal door, a metal door casing, a window pane, and a metal window casing, to name a few examples.
  • the structural component (B) is generally selected from the group consisting of a rigid molded, stamped or shaped metal article such as a steel, aluminum or thermoset polymer article, a metal door, a metal door casing, a window pane, and a metal window casing, to name a few examples.
  • Component (B) can be coated or non-coated for example in a painted automotive body panel, a RIM molded thermoset polymeric article in the shape of a bumper.
  • Component (A) is most advantageously formed in the shape of an auto body side molding, weather seal profile, cove trim piece for pools and auto bumper fascia, to name a few examples.
  • Component (A) is a non structural component and does not have the capability to sustain stress loading. Structural component (B) must be joined with (A).
  • Component (A) comprises: a PVC miscible plasticizer, polyvinyl chloride homopolymer resin, and fibers.
  • the polyvinyl chloride exhibits a preferred intrinsic viscosity measured according to ASTM D1243 of from 0.4 to 0.9. Molecular weights in terms of inherent viscosity of between 0.5 and 0.7 exhibit the best combination of melt strength and flowability.
  • the preferred (A) component has poorer sag strength than materials taught in EP 411 429, and is not as useful for structural strength.
  • Plasticizer is present at a level of from about 15 weight parts to about 150 weight parts per 100 weight parts polyvinyl halide resin in (A).
  • Plasticizer is preferably present in (A) at from 20 weight parts to 55 weight parts per 100 weight parts polyvinyl halide in (A).
  • Fibrous reinforcing material can be selected from the group consisting of chopped glass fibers and polymeric fibers, such as aramid, polyamide, polymethacrylate, fibrous derivatives of cellulose non-glass fibers are usable but less preferred for economic and technical reasons.
  • plasticizer component (A) can further contain a flexible polymeric material, for example, EVA, SBR, NBR, MBS, acrylic rubber, ABS, urethane, copolyester, styrenic block rubbers, any of which may or may not be completely miscible with PVC.
  • Component (A) exhibits among the lowest coefficient of linear thermal expansion per ASTM D696 of any material useful for molding of shaped plastics when sufficient amounts of plasticizer are used. Generally at least 15 weight parts per 100 weight parts
  • the plasticized PVC polymer will have a PVC phase having glass transition temperature of less than 50°C.
  • the plasticized PVC matrix has reduced tensile modulus measured per ASTM D638 compared with rigid fiber reinforced materials.
  • component (A) is joined with a structural component (B)
  • the strength and rigidity are not required in (A).
  • the plasticized, reinforced material exhibits significantly better dimensional stability as shown by CLTE and overcomes the lack of structural strength.
  • the amount of glass fibers generally can range from 3% to 50% by weight fiber reinforcement material. Dimensionally stability is further improved along with a balance of good properties when the glass fibers are present at from 10 to 30 percent by weight.
  • the preferred chopped glass fibers have a diameter of from about 8 to 25 microns and length of from 1 to 25 mm prior to combining with the thermoplastic. Upon incorporation into PVC, the glass fibers are broken leaving a variety of fiber lengths. Preferred glass fibers dimensions and 10-13 ⁇ m by 3-6 mm.
  • Optional particulate or platelet reinforcement material can also be combined with or can displace a quantity of fiber reinforcement and results in a non-structural material having CLTE of 4x10 "5 °K " ' or less and a good combination of physical properties.
  • the articles are shaped according to the forming method employed and exhibit a tensile modulus below that of reinforced rigid thermoplastic PVC, that is a modulus of from about 0.1 Gpa to about 0.5 Gpa.
  • the coefficient of linear thermal expansion for the preferred embodiments, per ASTM D696, is measured from -30°C to +30 °C and is found to preferredly lie in a range of from about O.lxlO "5 °K " ' to 4xl0 "5 °K " ', more preferably from l.OxlO "5 °K " ' to 2.9xl0 "5 °K " ', and still more preferably from l.OxlO "5 °K ' ' to 2.0xl0 "5 °K- ⁇
  • a composite comprising an extruded non-structural component (A) as above which exhibits a coefficient of linear thermal expansion of from O.lxlO "5 °K " ' to 4xl0 "5 K “1 .
  • (A) is prepared by subjecting the (A) compound to an extrusion process whereby a shaped profile is formed which conforms to the cross-section of the extruder die.
  • the preferred extruded non-structural articles are elongated and have an aspect ratio of length to width of at least 2, preferably 4, more preferably about 6 to 50 or more.
  • the fiber orientation provides an improved CLTE in the axial direction, and the magnitude of lineal expansion is desirably very low.
  • a composite article containing non- structural component (A) formed by injection molding process has excellent dimensional stability.
  • the compound is formulated for high melt flowability and the molten material containing glass fibers adequately flows to fill the entire void in the mold.
  • the non-structural component (A) exhibits excellent dimensional stability and can be used in contact with rigid structural articles with tight size tolerance, without causing a distortion in the weaker component
  • Figure 1 is a log-log plot of tensile modulus (GPa) on the x-axis versus coefficient of linear thermal expansion ( X 10 "5 °K " ' ) (CLTE) for a variety of materials.
  • the triangular data points include metals, and rigid, fiber reinforced thermoplastics, as well as rigid non-reinforced thermoplastics.
  • the circular data points are measurements made from examples of the method of the present invention.
  • thermoplastic polymers or particulate reinforced thermoplastic exhibit higher coefficient of linear thermal expansion and relatively lower tensile modulus compared to a like polymer containing glass reinforcement.
  • Al metals aluminum
  • Mg magnesium
  • Cu Copper
  • SS stainless steel
  • carbon steel steel
  • the composite containing non-structural component (A) can have a close match of the CLTE of the structural component (B) to which it is attached.
  • non- structural uses are uses where an article does not bear sustained load stress. Sufficient internal stresses would lead to permanent distortion or creep for the non-structural component (A) if it were not for the excellent dimensional stability.
  • the non-structural component (A) can be tightly attached to the structural component (B) and maintain adherence over a wide temperature range and under prolonged thermal cycling without weakening or compromising the attachment means.
  • the plasticized matrix material must exhibit a dominant PVC phase morphology. Those materials which reduce the modulus in a blend with PVC but which are immiscible with PVC are less preferred in the present invention. A combination of PVC miscible plasticizer and non-miscible polymer is however useful. Miscibility herein means that the plasticized matrix must exhibit a Tg which is lower that of a rigid matrix PVC.
  • the matrix may also include lubricants processing aids and at least one stabilizer for PVC. Impact modifiers are not generally required but may be used.
  • the plotted data point for example A in figure 1 represents the measured properties obtained by combining 35 weight parts of plasticizer with polyvinyl chloride (100 wt. parts) having an inherent viscosity of 0.68.
  • the CLTE of example A was 3.1 xlO "5 °K ' 1 and is lower than rigid unplasticized PVC shown in figure 1 having a CLTE of 3.2 xlO '5 °K ' '.
  • the modulus of example A was 1.4 GPa versus 5.1 GPa for rigid, glass reinforced, unplasticized PVC.
  • Example B plotted in figure 1 resulted from the combination of 100 wt. parts PVC (I.V. 0.52) with 10 parts of polyacrylate processing aid and 35 parts of mixed alkyl (C 7 -
  • Co-C n Co-C n ) phthalate plasticizer, stabilizer, lubricants, and an amount of 0.25 x 13 micron glass fibers sized with aminosilane coupling agent such that the total composition contained 30% by weight of glass fibers.
  • modulus of example B has been reduced below that of rigid GFPVC but is higher than example A; and the CLTE is also favorably identical to the CLTE of aluminum.
  • Aluminum can be used as a substrate for this article over a broad temperature range.
  • Example C represents the combination of 52 weight parts of plasticizer in a compound similar to example B, but having glass fiber content of 20% by weight. There is noted a still further reduction in CLTE versus example B due to the additional plasticizer even though the amount of glass content is 20% by weight in C versus 30% by weight in B. The modulus of C is reduced from 1.9 GPa to 0.79 GPa, yet the magnitude of tensile modulus is not of primary concern for the aforementioned uses.
  • Example D contains a still lower CLTE than example C yet has a higher tensile modulus as C and for some uses this a more desirable combination of properties.
  • Table 1 are listed the weight percent glass fiber content and parts plasticizer per 100 weight parts PVC resin for the examples A-K plotted in figure 1.
  • Examples E and G have a CLTE below GFPVC.
  • increasing the level of plasticizer from 74 to 82 phr, at a fixed weight percent glass content causes a reduction in the coefficient of linear thermal expansion.
  • the plasticizer content of 35 or 52 parts per 100 parts PVC yields a 30% glass fiber reinforced PVC composite having a reduced CLTE.
  • the above examples each contained polyvinyl chloride homopolymer having an I.V. ranging from 0.5 to 1.1, a stabilizer such as an organotin or a mixed metal soap type, such as a barium-zinc stabilizer. Preferred stabilizers are mixed metal types. The amount of thermal stabilizer used can range from 1 to 5 weight parts.
  • There can be included other conventional additives such as processing aids, or impact modifiers, pigments or colorants, UV stabilizers and co-stabilizers known in the compounding art. Impact modifiers are not generally need because of the inherent toughness of the plasticized matrix.
  • the articles exhibit Izod impact strength of at least 1 ft-lb per inch of notch.
  • Preferred processing aids are polyacrylates, for example those commercially available from Rohm and Haas, Inc. under the Paraloid trademark. Most preferred processing aids are styrene-acrylonitrile copolymers.
  • the conventional lubricant waxes, polyol esters, and fatty soaps can be used.
  • the preferred lubricant is a silicate type, in which the resulting surface tension of the surface of a shaped article is higher than 35 dynes/cm, preferably 45 dynes/cm and most preferably from 45 to 65 dynes/cm 2 in order provide improved adhesion to coatings or applied films.
  • In-mold transfer of films during formation is a preferred method of joining one side of the non-structural article to appearance films such as pigmented non-reinforced flexible PVC films.
  • Amounts of from 2 to about 15 weight parts of lubricant can be used, with the type and amount of lubricant and stabilizer depending on factors beyond the scope of this invention.
  • any of the conventional processes for making PVC polymers such as mass, suspension, solution or emulsion polymerization methods can be used. Mass and suspension polymerization methods are the preferred processes. Suspension polymers are most preferred. Porous, commercial suspension grade homopolymer PVC having an I.V. of from 0.4 to 0.85 are preferred with the more preferred PVC polymers having an I.V. of from 0.5 to 0.7. Generally the molecular weight is controlled by the polymerization temperature and/or by the use of chain transfer agents.
  • the PVC polymer can be a copolymer of vinyl chloride and terminally unsaturated comonomer(s), it is essential that the PVC resin be a rigid polymer in the unplasticized state, the preferred type of rigid polymers being a homopolymer of polyvinyl chloride. In the present invention, homopolymers maintain better physical properties in the plasticized state such as higher strength and modulus. Homopolymers or copolymers of PVC having an unplasticized modulus of elasticity of greater than 100,000 pounds per square inch per ASTM-D747 are essential for use in the present invention.
  • flexible copolymers of PVC having a Tg in the unplasticized state of less than about 60 °C and having an unplasticized modulus for less than 100,000 p.s.i. are not suitable in the present invention.
  • Block copolymers of homopolymer PVC may be suitable, provided there is a major predominant phase of rigid polyvinyl halide polymer which would meet the above modulus criteria.
  • the use of flexible copolymers obviates the ability to add sufficient plasticizer to produce the CLTE lowering effect and therefore are outside the scope of the invention.
  • the miscible plasticizer forms a single phase, single Tg PVC matrix and is incorporated at a level of from about 5 weight parts to about 150 weight parts per 100 weight parts polyvinyl chloride resin, the amount in any embodiment depending on the modulus and CLTE desired. More preferably, plasticizer is incorporated at 20 weight parts to 65 weight parts per 100 weight parts polyvinyl chloride.
  • the formulations of the invention must have adequate melt flowability, usually evaluated by the spiral flow test.
  • Spiral flow is a measure of the extent of injection melt flow under a fixed ram force input.
  • the extent of spiral flow provides a prediction of the limitations in size and configuration of injection molding dies suitable for a given resin compound.
  • the test employs a graduated 60-inch spiral flow mold with a standard cross section die such as a 1/8 inch by 3/16 inch rectangular cross section die used in conjunction with a Van Dorn injection molding machine. Generally, the mold temperature is set at 55°C, the injection melt pressure is a constant psi, with a constant injection time, clamp time, and mold open time, giving a constant total cycle time. A screw of specified diameter and L/D is used.
  • Stock temperature at the nozzle is standardized also. Spiral flow is proper when the polymer is able to flow into the pattern of the mold used.
  • the extent of spiral flow varied depending on the molecular weight of the plasticizer, the molecular weight of the polyvinyl halide polymer as well as the amount of reinforcement or other material employed.
  • a desirable spiral flow is at least 15 inches, preferably at least 25 inches, more preferably at least 35 inches, and most preferably at least 40 inches. Contrary to conventional wisdom, it has been found that relatively low molecular weight polyvinyl chloride having an I.V. of from 0.4 to 0.85 works better in the present invention than PVC having molecular weight of 0.9 or above.
  • the plasticizers used in this invention are PVC miscible plasticizers to the extent that a single phase morphology results in combination with PVC. These include those taught in The Technology of Plasticizers, Sears and Darby, John Wiley and Sons, New York (1982) ch.4, inco ⁇ orated herein by reference.
  • a suitable plasticizer may be polymeric, or monomeric such as a high Tg solid or a low Tg material but there must be a degree of miscibility such that a single phase, single Tg results from their combination.
  • the preferred plasticizers are liquids.
  • the amount of plasticizer employed is the minimum amount necessary to reduce the CLTE to 4 xlO "5 °K " ' or less.
  • polyesters with molecular weight below 10,000 especially those derived from glutaric or sebacic acid
  • plasticizers include the phthalates, trimellitates, epoxides, aliphatic diesters, and phosphates, including mixtures.
  • Preferred are the phthalates trimellitates and epoxides.
  • preferred phthalates include dioctyl phthalate, diisooctyl phthalate, diisodecylphthalate; and mixed alkyl esters such as heptyl, nonyl and undecyl phthalate.
  • Preferred trimellitates are tri-octyl trimellitate and tri-isononyl trimellitate.
  • the preferred epoxides include epoxidized soybean oil, and epoxidized linseed oil.
  • a single plasticizer can be employed, as well as blends of more than one miscible plasticizer.
  • An example of a preferred blend is a blend of 85 parts per hundred parts resin of dioctyl phthalate and 5 parts per hundred parts resin of epoxidized soybean oil.
  • the amount of fiber reinforcement used ranges from about 3 weight percent to about 50 weight percent of the non-structural component (A). Preferably from about 6 weight percent to about 35 weight percent and more preferably from 10%. The most preferred amount of fiber reinforcement material present depends on the particular combination of properties desired as these properties can be accurately tailored to suit the requirements.
  • suitable fiber reinforcement materials include the various glass fiber types, such as E-glass, with or without coupling agents inco ⁇ orated thereon, either as mats, woven or non woven fibers or chopped; stainless steel shavings; polymeric fibers, such as aramid or cellulosic fibers, and combinations of more than one type of fiber.
  • the preferred fiber reinforcing material has a diameter of greater than or equal to 8 microns, preferably 10 to 13 microns, more preferably at least 12 microns and most preferably about 13 microns, and a length of 1/8" (3 mm) or 1/4" (6 mm). Alternatively, a particular or platelet filler, or both can be included.
  • An example is the combination of glass and mineral filler, the mineral filler being either of spherical or platelet shape.
  • a particulate filler such as calcium carbonate and platelet reinforcement fillers such as mica or talc are exemplary types.
  • Preferred combinations of fiber and platelet reinforcing filler are 30% fiber and 10% platelet, and 20% fiber and 20% platelet, each respectively.
  • the glass used in this invention can be sized or non-sized.
  • a preferred sizing and coupling agent are disclosed in U.S. Patent 4,536,360 to Rahrig, inco ⁇ orated herein by reference which describes the use of aminosilane coupling inco ⁇ orated into a sizing containing a film former which is more basic than polyvinyl acetate.
  • Preferred film formers are polyethers, and silylated polyazamides. Higher physical properties are seen when diaminosilane and preferred film formers are present on the glass fibers.
  • component (A) it is preferred to first mix plasticizer with the polyvinyl chloride resin in the initial compounding step. Fiber reinforcement material is added subsequently. As a result of the mixing, the reinforcement material, whether initially in long glass fibers or not, will be crushed and broken, and will be dispersed relatively uniformly throughout the mixture.
  • a specific method of preparation of the composite comprises combining PVC, process aid, plasticizer, stabilizer, filler or pigment, if used, and lubricants in a Henschel mixer.
  • the powder mixture can be fluxed under heat and shear in a Buss reciprocating extruder. Is preferred to equip the extruder with a hopper and feeding screw through which the glass fibers are added.
  • the polymer compound and glass mixture is then sheared to uniformly disperse the glass throughout the melt.
  • the mixture can be formed into pellets and later molded, extruded, and shaped in any conventional process for forming shaped thermoplastic articles.
  • the articles will generally be formed at temperatures high enough to induce melt flow under pressure.
  • the temperatures and work level employed are high enough to fuse the resin particles and ensure complete plasticization of the matrix.
  • the pressure should be high enough to extrude an article, or inject the molten composition into a mold pattern, co-extrude a composite article, or co-inject the material with another thermoplastic component such as a dissimilar plastic substrate.
  • temperatures range from about 175°C to about 235°C, and preferably from about 180°C to about 210°C.
  • the pressures are generally those encountered in injection molding and extrusion, co- extrusion, co-injection or laminating processes.
  • the composition is also useful in compression molding, although this process is not favored as a commercial process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention se rapporte à un article composite combiné, constitué par un élément non structurel (A) joint à un élément structurel (B). L'élément non structurel ne supporte pas de contrainte de charge soutenue, en raison de sa jointure à l'élément structurel (B). L'élément non structurel (A) comprend une résine d'halogénure polyvinylique plastifiée, ainsi que des fibres telles que des fibres de verre. Le plastifiant et les fibres sont présents en quantité suffisante pour produire un coefficient d'expansion thermique linéaire résultante compris entre 0,1x10-5 °K-1 et 4x10-5 °K-1. L'élément structurel (B) est généralement choisi dans le groupe constitué par un article en métal rigide moulé, frappé ou façonné, tel qu'un article en polymère thermodurcissable, en acier ou en aluminium, une porte métallique, un châssis de porte métallique, une vitre et un bâti de fenêtre métallique, pour ne citer que quelques exemples. L'élément structurel (B) peut être recouvert ou non d'un revêtement, par exemple dans un panneau de carrosserie d'automobile peint, un article en polymère thermodurcissable moulé R.M.I. ayant la forme d'un pare-choc. Cet article composite combiné est particulièrement utile dans des applications où les températures d'utilisation varient considérablement, par exemple dans des éléments d'enjoliveur d'automobile, et des éléments de construction, tels que structures de portes et fenêtres et pièces d'espacement, nécessitant une fixation permanente à l'élément ou aux éléments structurel(s).
PCT/US1994/004679 1993-05-03 1994-04-28 Articles en pvc thermoplastique renforce de dimensions stables Ceased WO1994025272A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR9406364A BR9406364A (pt) 1993-05-03 1994-04-28 Artigo compósito e processo de produção do mesmo
AU67770/94A AU6777094A (en) 1993-05-03 1994-04-28 Dimensionally stable reinforced thermoplastic pvc articles
JP6524538A JPH08509673A (ja) 1993-05-03 1994-04-28 寸法安定な強化熱可塑性ｐｖｃ製品
KR1019950704916A KR960702384A (ko) 1993-05-03 1994-04-28 치수안정성 강화 열가소성 pvc 물품(dimensionally stable reinforced thermoplastic pvc articles)
EP94915929A EP0696963A1 (fr) 1993-05-03 1994-04-28 Articles en pvc thermoplastique renforce de dimensions stables

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US5633993A 1993-05-03 1993-05-03
US08/056,339 1993-05-03

Publications (1)

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WO1994025272A1 true WO1994025272A1 (fr) 1994-11-10

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EP (1) EP0696963A1 (fr)
JP (1) JPH08509673A (fr)
KR (1) KR960702384A (fr)
AU (1) AU6777094A (fr)
BR (1) BR9406364A (fr)
CA (1) CA2161330A1 (fr)
WO (1) WO1994025272A1 (fr)

Cited By (25)

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EP3771700A1 (fr) * 2019-08-02 2021-02-03 Corning Incorporated Ensembles de verre formés à froid et leurs procédés de fabrication
US11292343B2 (en) 2016-07-05 2022-04-05 Corning Incorporated Cold-formed glass article and assembly process thereof
US11331886B2 (en) 2016-06-28 2022-05-17 Corning Incorporated Laminating thin strengthened glass to curved molded plastic surface for decorative and display cover application
US11332011B2 (en) 2017-07-18 2022-05-17 Corning Incorporated Cold forming of complexly curved glass articles
CN114573869A (zh) * 2022-03-17 2022-06-03 浙江传化华洋化工有限公司 钡锌液体稳定剂及其应用
US11384001B2 (en) 2016-10-25 2022-07-12 Corning Incorporated Cold-form glass lamination to a display
US11459268B2 (en) 2017-09-12 2022-10-04 Corning Incorporated Tactile elements for deadfronted glass and methods of making the same
US11518146B2 (en) 2018-07-16 2022-12-06 Corning Incorporated Method of forming a vehicle interior system
US11550148B2 (en) 2017-11-30 2023-01-10 Corning Incorporated Vacuum mold apparatus, systems, and methods for forming curved mirrors
US11586306B2 (en) 2017-01-03 2023-02-21 Corning Incorporated Vehicle interior systems having a curved cover glass and display or touch panel and methods for forming the same
US11597672B2 (en) 2016-03-09 2023-03-07 Corning Incorporated Cold forming of complexly curved glass articles
US11660963B2 (en) 2017-09-13 2023-05-30 Corning Incorporated Curved vehicle displays
US11685685B2 (en) 2019-07-31 2023-06-27 Corning Incorporated Method and system for cold-forming glass
US11685684B2 (en) 2017-05-15 2023-06-27 Corning Incorporated Contoured glass articles and methods of making the same
US11718071B2 (en) 2018-03-13 2023-08-08 Corning Incorporated Vehicle interior systems having a crack resistant curved cover glass and methods for forming the same
US11745588B2 (en) 2017-10-10 2023-09-05 Corning Incorporated Vehicle interior systems having a curved cover glass with improved reliability and methods for forming the same
US11767250B2 (en) 2017-11-30 2023-09-26 Corning Incorporated Systems and methods for vacuum-forming aspheric mirrors
US11768369B2 (en) 2017-11-21 2023-09-26 Corning Incorporated Aspheric mirror for head-up display system and methods for forming the same
US11772361B2 (en) 2020-04-02 2023-10-03 Corning Incorporated Curved glass constructions and methods for forming same
US11772491B2 (en) 2017-09-13 2023-10-03 Corning Incorporated Light guide-based deadfront for display, related methods and vehicle interior systems
US11899865B2 (en) 2017-01-03 2024-02-13 Corning Incorporated Vehicle interior systems having a curved cover glass and a display or touch panel and methods for forming the same
US12140732B2 (en) 2018-03-02 2024-11-12 Corning Incorporated Anti-reflective coatings and articles and methods of forming the same
US12235477B2 (en) 2018-07-12 2025-02-25 Corning Incorporated Deadfront configured for color matching
US12466756B2 (en) 2019-10-08 2025-11-11 Corning Incorporated Curved glass articles including a bumper piece configured to relocate bending moment from display region and method of manufacturing same
US12487691B2 (en) 2023-09-05 2025-12-02 Corning Incorporated Vehicle interior systems having a curved cover glass and display or touch panel and methods for forming the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5470379A (en) * 1977-11-15 1979-06-06 Matsushita Electric Works Ltd Synthetic resin sheet
US4313985A (en) * 1978-12-04 1982-02-02 Inoue Gomu Kogyo Kabushika Kaisha Plastic auto part and its manufacturing process
JPS60177054A (ja) * 1984-02-21 1985-09-11 Sekisui Chem Co Ltd 塩化ビニル系樹脂組成物
JPS60179444A (ja) * 1984-02-27 1985-09-13 Sekisui Chem Co Ltd 塩化ビニル系樹脂組成物
JPS60192747A (ja) * 1984-03-15 1985-10-01 Sekisui Chem Co Ltd 塩化ビニル系樹脂成形品及びその成形方法
JPS60192748A (ja) * 1984-03-15 1985-10-01 Sekisui Chem Co Ltd 塩化ビニル系樹脂組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5470379A (en) * 1977-11-15 1979-06-06 Matsushita Electric Works Ltd Synthetic resin sheet
US4313985A (en) * 1978-12-04 1982-02-02 Inoue Gomu Kogyo Kabushika Kaisha Plastic auto part and its manufacturing process
JPS60177054A (ja) * 1984-02-21 1985-09-11 Sekisui Chem Co Ltd 塩化ビニル系樹脂組成物
JPS60179444A (ja) * 1984-02-27 1985-09-13 Sekisui Chem Co Ltd 塩化ビニル系樹脂組成物
JPS60192747A (ja) * 1984-03-15 1985-10-01 Sekisui Chem Co Ltd 塩化ビニル系樹脂成形品及びその成形方法
JPS60192748A (ja) * 1984-03-15 1985-10-01 Sekisui Chem Co Ltd 塩化ビニル系樹脂組成物

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8543, Derwent World Patents Index; AN 85-265841 *
DATABASE WPI Week 8543, Derwent World Patents Index; AN 85-266883 *
DATABASE WPI Week 8545, Derwent World Patents Index; AN 85-281033 *
DATABASE WPI Week 8545, Derwent World Patents Index; AN 85-281034 *
PATENT ABSTRACTS OF JAPAN vol. 3, no. 91 (C - 054) 3 August 1979 (1979-08-03) *

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US11597672B2 (en) 2016-03-09 2023-03-07 Corning Incorporated Cold forming of complexly curved glass articles
US11331886B2 (en) 2016-06-28 2022-05-17 Corning Incorporated Laminating thin strengthened glass to curved molded plastic surface for decorative and display cover application
US11338556B2 (en) 2016-06-28 2022-05-24 Corning Incorporated Laminating thin strengthened glass to curved molded plastic surface for decorative and display cover application
US12472726B2 (en) 2016-06-28 2025-11-18 Corning Incorporated Laminating thin strengthened glass to curved molded plastic surface for decorative and display cover application
US11292343B2 (en) 2016-07-05 2022-04-05 Corning Incorporated Cold-formed glass article and assembly process thereof
US11850942B2 (en) 2016-07-05 2023-12-26 Corning Incorporated Cold-formed glass article and assembly process thereof
US11607958B2 (en) 2016-07-05 2023-03-21 Corning Incorporated Cold-formed glass article and assembly process thereof
US11384001B2 (en) 2016-10-25 2022-07-12 Corning Incorporated Cold-form glass lamination to a display
US11586306B2 (en) 2017-01-03 2023-02-21 Corning Incorporated Vehicle interior systems having a curved cover glass and display or touch panel and methods for forming the same
US12386446B2 (en) 2017-01-03 2025-08-12 Corning Incorporated Vehicle interior systems having a curved cover glass and display or touch panel and methods for forming the same
US11899865B2 (en) 2017-01-03 2024-02-13 Corning Incorporated Vehicle interior systems having a curved cover glass and a display or touch panel and methods for forming the same
US11685684B2 (en) 2017-05-15 2023-06-27 Corning Incorporated Contoured glass articles and methods of making the same
US12122236B2 (en) 2017-07-18 2024-10-22 Corning Incorporated Cold forming of complexly curved glass articles
US11332011B2 (en) 2017-07-18 2022-05-17 Corning Incorporated Cold forming of complexly curved glass articles
US11459268B2 (en) 2017-09-12 2022-10-04 Corning Incorporated Tactile elements for deadfronted glass and methods of making the same
US12110250B2 (en) 2017-09-12 2024-10-08 Corning Incorporated Tactile elements for deadfronted glass and methods of making the same
US11713276B2 (en) 2017-09-12 2023-08-01 Corning Incorporated Tactile elements for deadfronted glass and methods of making the same
US12012354B2 (en) 2017-09-12 2024-06-18 Corning Incorporated Deadfront for displays including a touch panel on decorative glass and related methods
US11772491B2 (en) 2017-09-13 2023-10-03 Corning Incorporated Light guide-based deadfront for display, related methods and vehicle interior systems
US11660963B2 (en) 2017-09-13 2023-05-30 Corning Incorporated Curved vehicle displays
US11919396B2 (en) 2017-09-13 2024-03-05 Corning Incorporated Curved vehicle displays
US11745588B2 (en) 2017-10-10 2023-09-05 Corning Incorporated Vehicle interior systems having a curved cover glass with improved reliability and methods for forming the same
US12103397B2 (en) 2017-10-10 2024-10-01 Corning Incorporated Vehicle interior systems having a curved cover glass with improved reliability and methods for forming the same
US11768369B2 (en) 2017-11-21 2023-09-26 Corning Incorporated Aspheric mirror for head-up display system and methods for forming the same
US11550148B2 (en) 2017-11-30 2023-01-10 Corning Incorporated Vacuum mold apparatus, systems, and methods for forming curved mirrors
US11767250B2 (en) 2017-11-30 2023-09-26 Corning Incorporated Systems and methods for vacuum-forming aspheric mirrors
US12140732B2 (en) 2018-03-02 2024-11-12 Corning Incorporated Anti-reflective coatings and articles and methods of forming the same
US11718071B2 (en) 2018-03-13 2023-08-08 Corning Incorporated Vehicle interior systems having a crack resistant curved cover glass and methods for forming the same
US12235477B2 (en) 2018-07-12 2025-02-25 Corning Incorporated Deadfront configured for color matching
US11518146B2 (en) 2018-07-16 2022-12-06 Corning Incorporated Method of forming a vehicle interior system
US12296556B2 (en) 2018-07-16 2025-05-13 Corning Incorporated Vehicle interior systems having a cold-bent glass substrate and methods for forming the same
US11685685B2 (en) 2019-07-31 2023-06-27 Corning Incorporated Method and system for cold-forming glass
EP3771700A1 (fr) * 2019-08-02 2021-02-03 Corning Incorporated Ensembles de verre formés à froid et leurs procédés de fabrication
US12466756B2 (en) 2019-10-08 2025-11-11 Corning Incorporated Curved glass articles including a bumper piece configured to relocate bending moment from display region and method of manufacturing same
US11772361B2 (en) 2020-04-02 2023-10-03 Corning Incorporated Curved glass constructions and methods for forming same
US12011914B2 (en) 2020-04-02 2024-06-18 Corning Incorporated Curved glass constructions and methods for forming same
CN114573869B (zh) * 2022-03-17 2023-10-13 浙江传化华洋化工有限公司 钡锌液体稳定剂及其应用
CN114573869A (zh) * 2022-03-17 2022-06-03 浙江传化华洋化工有限公司 钡锌液体稳定剂及其应用
US12487691B2 (en) 2023-09-05 2025-12-02 Corning Incorporated Vehicle interior systems having a curved cover glass and display or touch panel and methods for forming the same

Also Published As

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KR960702384A (ko) 1996-04-27
JPH08509673A (ja) 1996-10-15
EP0696963A1 (fr) 1996-02-21
CA2161330A1 (fr) 1994-11-10
BR9406364A (pt) 1996-02-13
AU6777094A (en) 1994-11-21

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