GB1592310A - Creación de Inventos y Patentes con Inteligencia Artificial

GB1592310A – Glass fibre reinforced thermoplastic resin moulding material
– Google Patents

GB1592310A – Glass fibre reinforced thermoplastic resin moulding material
– Google Patents
Glass fibre reinforced thermoplastic resin moulding material

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Publication number
GB1592310A

GB1592310A
GB14593/78A
GB1459378A
GB1592310A
GB 1592310 A
GB1592310 A
GB 1592310A
GB 14593/78 A
GB14593/78 A
GB 14593/78A
GB 1459378 A
GB1459378 A
GB 1459378A
GB 1592310 A
GB1592310 A
GB 1592310A
Authority
GB
United Kingdom
Prior art keywords
resin
thermoplastic resin
molding material
glass fiber
styrene
Prior art date
1978-04-13
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.)

Expired

Application number
GB14593/78A
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.)

Asahi Dow Ltd

Original Assignee
Asahi Dow Ltd
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.)
1978-04-17
Filing date
1978-04-13
Publication date
1981-07-01

1978-04-13
Application filed by Asahi Dow Ltd
filed
Critical
Asahi Dow Ltd

1981-07-01
Publication of GB1592310A
publication
Critical
patent/GB1592310A/en

1982-05-03
Priority to HK18382A
priority
Critical
patent/HK18382A/en

Status
Expired
legal-status
Critical
Current

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Classifications

B—PERFORMING OPERATIONS; TRANSPORTING

B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL

B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL

B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials

B05D7/20—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wires

B—PERFORMING OPERATIONS; TRANSPORTING

B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL

B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS

B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 – B29B13/00

B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 – B29B13/00 of reinforcements or fillers

B29B15/10—Coating or impregnating independently of the moulding or shaping step

B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length

B—PERFORMING OPERATIONS; TRANSPORTING

B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL

B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS

B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 – B29B13/00

B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 – B29B13/00 of reinforcements or fillers

B29B15/10—Coating or impregnating independently of the moulding or shaping step

B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length

B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex

B—PERFORMING OPERATIONS; TRANSPORTING

B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL

B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS

B29B9/00—Making granules

B29B9/02—Making granules by dividing preformed material

B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion

B—PERFORMING OPERATIONS; TRANSPORTING

B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL

B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS

B29B9/00—Making granules

B29B9/12—Making granules characterised by structure or composition

B29B9/14—Making granules characterised by structure or composition fibre-reinforced

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

B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor

B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion

B29C48/04—Particle-shaped

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

B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor

B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts

B29C48/156—Coating two or more articles simultaneously

B—PERFORMING OPERATIONS; TRANSPORTING

B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL

B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING

B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts

B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics

B29C70/06—Fibrous reinforcements only

B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers

B29C70/086—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers and with one or more layers of pure plastics material, e.g. foam layers

B—PERFORMING OPERATIONS; TRANSPORTING

B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL

B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING

B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts

B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics

B29C70/06—Fibrous reinforcements only

B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres

B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length

B29C70/20—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres

B—PERFORMING OPERATIONS; TRANSPORTING

B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL

B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

B29K2105/00—Condition, form or state of moulded material or of the material to be shaped

B29K2105/0058—Liquid or visquous

B29K2105/0064—Latex, emulsion or dispersion

B—PERFORMING OPERATIONS; TRANSPORTING

B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL

B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

B29K2105/00—Condition, form or state of moulded material or of the material to be shaped

B29K2105/0058—Liquid or visquous

B29K2105/0073—Solution

B—PERFORMING OPERATIONS; TRANSPORTING

B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL

B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

B29K2105/00—Condition, form or state of moulded material or of the material to be shaped

B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts

B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns

B29K2105/10—Cords, strands or rovings, e.g. oriented cords, strands or rovings

B29K2105/101—Oriented

B29K2105/108—Oriented arranged in parallel planes and crossing at substantial angles

B—PERFORMING OPERATIONS; TRANSPORTING

B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL

B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

B29K2709/00—Use of inorganic materials not provided for in groups B29K2703/00 – B29K2707/00, for preformed parts, e.g. for inserts

B29K2709/08—Glass

B—PERFORMING OPERATIONS; TRANSPORTING

B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL

B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds

B29K2995/0037—Other properties

B29K2995/005—Oriented

B29K2995/0051—Oriented mono-axially

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/249921—Web or sheet containing structurally defined element or component

Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity

Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix

Y10T428/249942—Fibers are aligned substantially parallel

Y10T428/249946—Glass fiber

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Y10T428/2913—Rod, strand, filament or fiber

Y10T428/2933—Coated or with bond, impregnation or core

Y10T428/2938—Coating on discrete and individual rods, strands or filaments

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Y10T428/2913—Rod, strand, filament or fiber

Y10T428/2933—Coated or with bond, impregnation or core

Y10T428/2964—Artificial fiber or filament

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Y10T428/2991—Coated

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Y10T428/2991—Coated

Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Y10T428/2996—Glass particles or spheres

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Y10T428/2991—Coated

Y10T428/2998—Coated including synthetic resin or polymer

Description

PATENT SPECIFICATION ( 11) 1592310
0 ( 21) Application No 14593/78 ( 22) Filed 13 April 1978 ( 44) Complete Specification published 1 July 1981 ( 199))1: i
CQ ( 51) INT CL 3 DOID 11/06; B 29 F 3/10; D 04 H 1/58, 1/74, 3/04, 3/12; / C ( 52) Index at acceptance B 5 A 1 R 214 E 1 R 214 F IR 314 C 1 A 1 R 314 C 1 C l R 314 C 1 D 1 R 314 C 1 E IR 314 C 1 F 1 R 314 C 1 S 1 R 314 C 1 X 1 R 314 C 6 1 R 322 20 T 14 20 T 17 2 A 4 F 2 B 1 2 D 1 X B 11 T 22 P D 1 W 4 X 6 ( 72) Inventors KICHIYA TAZAKI, TAMOTSU TAHARA, AKIHIRO WADA and YUKIHISA MIZUTANI ( 54) GLASS FIBER REINFORCED THERMOPLASTIC RESIN MOLDING MATERIAL ( 71) We, ASAHI-DOW LIMITED, a corporation organised under the laws of Japan, of 1-2, Yurakucho 1-chome, Chiyoda-ku, Tokyo, Japan, do hereby declare the invention, for which we pray that a patent may be granted to Us, and the method by which it is to be performed, to be particularly described in and by the following statement: 5
This invention relates to an improved molding material of a glass fibercontaining thermoplastic resin composition which is capable of producing molded articles in which glass fibers are dispersed uniformly in the resin matrix with longer average fiber length than hitherto to improve various properties of molded articles, said material being also improved in procesing characteristics and substantially free 10 from such problems as damaging molding machines through frictional abrasion with the glass fibers contained therein, when compared with previous such materials.
Molded articles of glass fiber reinforced thermoplastic resins have been used as useful molding materials having excellent physical properties, especially 15 mechanical strength, as well as excellent moldability inherent in thermoplastic resins Since the oil crisis in 1973, they have further arrested attention as utilization of the material with higher added value and improvement of their physical properties has been keenly longed for In the prior art, these molded articles have been prepared especially by injection molding from various molding materials Among 20 them, a typical commercially available injection molding material for glass fiber reinforced thermoplastic products is constituted of chopped strands of a glass fiber dispersed in a thermoplastic resin, which is prepared by extrusion of a thermoplastic resin together with glass fibers Alternatively, another type of molding material having glass fiber core enclosed within a thermoplastic resin as outer 25 coating or shell is also known in the art, as disclosed by U S Patent 2, 877,501 and U.S Patent 3,608,033 The molding material of the former type, while it is advantageous in simple and easy preparation procedure, it is entirely impossible to have monofilaments with longer lengths dispersed uniformly throughout the resin Thus, this type of molding material can enjoy only limited reinforcing effect with glass 30 fibers inherent within such a structure On the other hand, in the latter type of molding material, the glass fibers are present as core in the central portion of the material covered with a uni-layer coating of a thermoplastic resin Consequently, the glass fibers fail to be uniformly dispersed in the resin when fabricated into a molded article Furthermore, with such a uni-layer coverage of glass fibers, the 35 molding material cannot be free from the problem of damaging mechanical parts at the time of molding because glass fibers exposed by disintegratiori of outer shell are directly contacted with such mechanical parts.
According to the present invention, there is provided a molding material which comprises ( 1) at least one inner rod-shaped body, each comprising a bundle 40 of glass fiber filaments and a non-oriented thermoplastic resin, the glass fiber filaments being respectively separated from each other and extending parallel to each other through the non-oriented resin and ( 2) an outer covering layer of an oriented thermoplastic resin which is substantially oriented in the axial direction of the glass fiber filaments and compatible with the non-oriented thermoplastic resin in the inner rod-shaped body.
The molding material of the present invention may be better understood with reference to the accompanying drawings, in which:
Fig I is a cross-sectional view across the longitudinal axis of one embodiment 5 of the present invention shaped as a cylindrical pellet, in which there are five inner rods of a thermoplastic resin containing glass fiber filaments embedded in an outer covering layer of thermoplastic resin; Fig 2 is a perspective, sectional view of the cylindrical pellet shown in Fig 1, taken along the line A-A in Fig 1, showing only the outer covering resin layer 10 portion from which the inner resin rods containing glass fiber filaments are removed; Fig 3 is a perspective view of an inner resin rod removed from the right cylindrical pellet as shown in Figs 1 and 2; Fig 4 a and b are schematic illustrations of the structures of prior art molding 15 materials, indicating the states of fracture thereof; Fig 5 is a flow sheet, illustrative schematically of the steps of the process for preparation of the molding material structure of the present invention; and Fig 6 is a longitudinal cross-sectional view of one example of a die to be used for preparation of the molding material of the present invention 20 As shown in Fig 1, at least one inner resin rod 2 containing a large number of glass mono-filaments 3 are embedded in outer covering resin layer l In one aspect, the inner thermoplastic resin rod in the present molding material is required to be non-oriented, while the outer covering thermoplastic resin layer is substantially oriented The terms «substantially oriented» and «non-oriented» used herein mean 25 whether or not there is substantial shrinkage of the resin in a cei tain direction when measured under conditions as hereinafter specified.
The inner thermoplastic resin rod 2 of the present structure contains a large number of glass monofilaments which extend parallel to each other through the resin rod in the longitudinal direction thereof, as shown in Fig 3 The resin in the 30 inner rod has an interseptal function for separating the filaments from each other so that the resultant molded article may contain uniformly dispersed glass fibers with longer length Such a structure of the inner rod is critical, because glass fibers which are not well separated from each other but contained as a bundle of filaments in the molding material will fail to be uniformly dispersed in the resultant 35 molded article The filaments 3 in the inner rod 2 may be derived conveniently from commercially available glass fiber rovings Such glass fiber rovings generally consist of from 500 to 20000 end filaments with diameters from 8 to 20 microns.
These glass rovings are usually treated with so called sizing compound, typically silicon type coupling agents, during manufacturing steps of glass fibers Most of the 40 presently available glass fiber rovings contain about 1 wt % of such a coupling agent, lubricant or sheafing agent The shape of the inner rod is not specifically limited insofar as such a large number of filaments of glass fiber can extend through the resin matrix separately in parallel to each other While its transverse crosssection is generally ellipsoidal or circular, it may also be otherwise such as 45 triangular, rectangular or polygonal The number of such inner rods may be variable from 1 to 40 or even higher, preferably from I to 10 depending on various conditions in the intended uses or preparation methods, but it is most preferably from 1 to 5.
As mentioned above, the outer covering resin layer 1 of the present molding 50 material structure is required to be substantially oriented in the axial direction of the glass fiber filaments contained in the inner resin rod as described above One of the advantages of the molding material of the present invention resides in that it causes little damage of mechanical parts during molding operations While being not bound by any theory, it is believed that such an effect is due to the specific 55 structure of the invention To speak of injection molding, pellets of a molding material are not still molten in the zone extending from feed zone to compression zone of a screw in an injection or extrusion molding machine but there occurs melting of pellets simultaneously with fracture thereof Frictional abrasion of metals such as screw or barrel is considered to be due to the friction with glass 60 fibers before the resin containing glass fibers is molten For example, in case of the blended glass fiber composition of the prior art, abrasion in the region from feed zone to compression zone is so great that after a month’s operation the injection molding machine may sometimes fail to give favorable molded articles In other words, at melting, kneading and measuring portions of the screw wherein the 65 I 1,592,310 2.
3 1,592,310 3.
thermoplastic resin is sufficiently molten to exhibit excellent lubricating effect, there occurs substantially no abrasion of screw or barrel The specific structure of the present invention serves to provide earlier melting of local sections of the thermoplastic resin around the glass fiber Namely, the outer covering resin layer which is oriented in the axial direction of glass fiber is liable to be readily broken in 5 the oriented direction (longitudinal fracture) through shearing force in the feed zone and compression zone of the screw As the result of such longitudinal fracture of the outer covering resin, the molding material is separated into the mass of the oriented outer layer and the inner rod containing glass fiber filaments enclosed within non-oriented thin layer resin (see Fig 2 and Fig 3) Thus, the inner resin rod 10 containing glass fiber filaments is removed from the outer covering resin layer and therefore the thin resin portion around the glass fiber is directly heated, without intermediary poorly thermoconductive resin layer, in the screw to be readily molten In contrast, as shown in Fig 4 (a), when the glass fiber is enclosed within only one non-oriented resin structure, it takes a long time before whole of a thick 15 resin portion around the fiber is molten and therefore the machine suffers from frictional abrasion of screw or barrel; furthermore, the fibers are also broken together with the resin, failing to give molded articles containing glass fibers with long average length On the other hand, as shown in Fig 4 (b), when a bundle of glass fiber filaments is enclosed only within an oriented resin, the glass fibers are 20 exposed as the result of longitudinal fracture of the oriented resin in the screw to be directly contacted with metals to cause friction.
In the molding material structure according to the present invention, the glass fiber content in the inner thermoplastic resin rod is preferably from 5 to 60 % by weight based on the total composition, the proportion of the non-oriented resin in 25 the inner rod is preferably from 0 25 to 18 % by weight and the proportion of the oriented resin in the outer covering resin layer is preferably from 94 75 to 22 % by weight, each being based on the total composition.
In the present invention, the thermoplastic resin to be used for the oriented outer covering resin layer is required to be compatible with the thermoplastic resin 30 to be used for the non-oriented resin rod The word «compatible» herein mentioned means that one resin contains common monomeric units contained in another resin or that there occurs no inter-layer peel-off between one resin and another The compatibility of typical combinations of the thermoplastic resins for use in the inner layer and-outer layer, respectively, are set forth in the following 35 Table 1:
1,592,310 TABLE 1:
PS AS ABS PPE PE PP POM PC PA PMMA PVC lonomer PS C AS N C ABS N C C PPE C N N C PE N N N N C PP N N N N C C POM N N N N N N C PC N C C C N N N C PA N N N N N N N N C PMMA N C C N N N N L N C PVC N N C N N N N N C C Ionomer N N N N C C L N C N N C (note) C = compatible, L = limitedly compatible and suitable for present process, N = non-compatible PS = polystyrene (including high-impact polystyrene); AS = acrylonitrile-styrene copolymer; ABS = acrylonitrile-butadiene-styrene copolymer (including methyl methacrylate-butadiene-styrene, methyl methacrylate-acrylonitrile-butadiene-styrene and acrylonitrile-butadiene-a-methyl-styrene-styrene copolymers); PPE = polyphenylene ether (including modified PPE); PE = polyethylene; PP = polypropylene; POM = polyoxymethylene; PC = polycarbonate; PA = polyamide; PMMA = polymethyl methacrylate; PVC = polyvinyl chloride.
\ O (l J C 0 xt tThe degree of orientation of the outer covering thermoplastic resin layer can easily be judged and tested by compression breaking of the molding material by means of, for example, pincers with muscular strength, etc to effect longitudinal fracture thereof By such a test method, the state of fracture in cylinders of a molding machine as mentioned above can easily be visualized More quantita 5 tively, however, the substantial orientation required for the outer thermoplastic resin layer is defined as having at least 0 5 % thermal shrinkage in the axial direction which is observed when the oriented resin, from which the non-oriented glass fiber containing inner rod(s) have been removed, is exposed to heat at a temperature 450 C higher than the Vicat softening point (ASTM-D-1525) of the oriented resin to for 30 minutes Such a degree of orientation can readily be imparted to the resin by extruding a molten resin through an extruder, followed by cooling.
The non-oriented thermoplastic resin in the inner rod as described above can generally be derived from an emulsion of a thermoplastic resin In order to permeate through mono-filaments of glass fiber roving, such an emulsion is is required to have affinity with glass fiber and a low viscosity of 100 centipoise or less For this purpose, it is preferred to use an aqueous emulsion having small particles of a thermoplastic resin dispersed in water When glass fiber roving is immersed in such an aqueous emulsion and dried, small particles of the resin are adhereed around each mono-filament of the glass fiber Such small particles of a 20 thermoplastic resin will form, even when molten at a high temperature to be fused with each other, a substantially non-oriented resin matrix.
The resin component in the non-oriented resin matrix is preferred to have a melt flow property (which depends primarily on molecular weight within the same kind of resins) which is the same as or superior to (i e smaller in molecular weight 25 than) that of the thermoplastic resin for the outer layer, so that dispersion of glass fibers in injection molded products obtained from the resultant molding material may be good to improve physical properties, e g Izod impact strength, by about 10 to 20 %.
The molding material of the present invention is not particularly limited in its 30 shape but inclusive of all shapes and sizes known in the art as pellets Preferably, however, it is shaped in cylinders with circular or ellipsoidal crosssections transverse to the axial direction of the glass fibers contained therein with shorter diameters ranging from 1 mm to 8 mm and longer diameters ranging from 1 mm to 15 mm, the length of the cylinders being preferably from 1 mm to 20 mm If 35 desired, other shapes including cylinders with triangular, rectangular, and polygonal cross-sections may also be employed.
There may be employed various methods for preparation of the molding material of the present invention as described above Referring now to a preferred embodiment of the process according to the present invention as illustrated in Fig 40 and 6, the process for preparation of the present molding material structure is described in detail below The process of the present invention comprises first treating at least one glass fiber roving comprising from 500 to 20000 end filaments with an aqueous emulsion of a thermoplastic resin to disperse each filament uniformly in said emulsion, followed by drying, to form an inner thermoplastic 45 resin rod containing the glass fiber monofilaments extending therethrough in parallel to each other separated by the thus formed non-oriented, thin interseptal resin and then extrusion coating on to one or more thus formed inner rod(s) another thermoplastic resin which is compatible with the thermoplastic resin of the inner rod to form an outer covering layer oriented in the direction of extrusion on the 50 non-oriented inner resin rod(s) and pelletizing the coated product into a suitable size of pellets.
One of the specific features of the process according to the present invention resides in pre-treatment of glass fiber roving with an emulsion of a thermoplastic resin which is compatible with the thermoplastic resin to be used for extrusion 55 coating As mentioned above, commercially available glass fiber roving generally employs a bundle of about 2,000 filaments, each filament being in the order of about 10 microns in diameter It is almost impossible in principle to coat each element of the filaments by extrusion coating of a highly viscous molten resin which is incompatible with glass fibers By treating a glass fiber roving which is hydro 60 philic in nature previously with an aqueous resin emulsion which is low in viscosity, each of the glass fiber filaments can be coated with said resin, thereby improving protection of the glass fibers as well as dispersibility (diffusion) of the glass fibers in the thermoplastic resin.
As shown in Fig 5, glass fiber roving 4 is led into pre-treatment liquid bath 5 to 65 I 1,592,310 s be immersed therein The pre-treatment liquid bath 5 is provided for coating an aqueous emulsion of a resin which is of the same kind as or compatible with the thermoplastic resin 13 supplied from the extruder 7 The aqueous resin emulsion is permitted to permeate into the glass fiber roving 4 while it is immersed in and passed through said liquid bath to thereby coating each element of glass fiber 5 mono-filaments with the aqueous resin emulsion to be adhered thereon.
Immersion of the glass fiber roving in said resin emulsion may simply be conducted by passing through said resin emulsion which is contained in a conventional liquid bath Alternatively, a vibrator such as ultrasonic vibrator is provided in said emulsion liquid bath so as to vibrate the emulsion, whereby the immersion 10 effect (coating adhesion effect) can be complete and production speed can also be accelerated.
The amount of the emulsion to be adhered by coating in the pre-treatment bath may be from 5 to 30 parts by weight as calculated as the resin content adhered after drying said emulsion, preferably 15 to 25 parts by weight, per 100 parts by 15 weight of the emulsion coated glass fiber roving after drying With an amount of less than 5 parts by weight, the glass fibers cannot completely be dispersed in the thermoplastic resin; while, an amount in excess of 30 parts by weight is difficult to be coated uniformly by once-through immersion For coating such a large amount of resin, adhesion by way of several times repeated coating or any other specific 20 device is required For the purpose of the present invention, no such specific concern is necessary.
The solid component (mainly resin component) in said resin emulsion may be within the range from 30 to 70 % by weight as is contained in conventional commercially available emulsions, thus requiring no specific emulsion to be used 25 The emulsion coated on the glass fiber roving 4 in the pre-treatment bath 5 is dried by a heater 6 The heater 6 may be any of those utilizing radiant heat such as nichrome wire heater, etc or those utilizing heated air Especially, when drying is conducted by use of a far infrared ray heater, utilization efficiency of electricity is good The internal atmosphere temperature in the heater 6 through which the glass 30 fiber roving 4 is passed may sufficiently be about 100 to 350 CC In case of some Iatices which are not good in heat-resistance and may cause irregularity through thermal shrinkage at higher temperatures such as SB latex, it is desired to effect drying at 100 to 1501 C.
The extruder may be any of conventionally used extruders for thermoplastic 35 resins, so long as it can feed stably a plastified molten resin without output irregulatity to a die 8 The extrusion die 8 is provided for the purpose of extrusion coating of the glass fiber roving It may be a die frequently used for wire coating, etc But, when five bundles of glass fiber roving are to be included within one pellet, for example, it is preferred to introduce five bundles of the emulsion treated 40 glass fiber roving as described above individually one by one into said die.
Furthermore, it is also preferred to have a die structure which enables another coating, namely twice (double) coating, of the five bundles by such a method as sheafing the five bundles at one spot in the die Double extrusion coating is preferable because glass fiber rovings, which usually consist of a bundle of 500 to 20000 45 ends of very fine filaments as mentioned above, are liable to be loosened to permit filaments exposed on the surface of the extrusion coated strand (linear body) if only one coating is applied The glass fibers exposed on the surface may be separated in the subsequent pelletizing step from the resin uue to insufficient adhesion to the resin, resulting in unfavorable scattering of such separated glass 50 fibers.
The die structure, which may differ depending on production speed, is preferably such that the pressure on the resin may be increased in the direction of the drawing force imposed on said coated strand, for example, the tapering mandrel and die shown in Fig 6 which shows one example of the extrusion coating die for 55 double coating This binds the bundles of filaments together and reduces the drawing force required.
The heater 6 and the die 8 should preferably be disposed such that the glass fiber roving dried and heated in the heater 6 may smoothly be introduced into the die 8 without abrupt flection and without too much cooling For, if a glass fiber 60 roving having 50 or more of the emulsion adhered, which is considerably rigid, is abruptly flexed, there is a risk that it may be broken to cause entanglement thereof at the inlet portion of the die.
The strand having glass fiber cores coated with a thermoplastic resin by the extrusion coating die 8 to a desired glass fiber content is cooled in a cooling water 65 b e m m r S d h e e i h e p r t e a m e t i q i d b a h 1 i p o v de 2 f r o a in O a 7 1,592,310 7 bath 9 to be solidified Rollers 10 feed the strand to a pelletizer (cutting machine) 11 where it is pelletized to a desired length The pellets are stocked up in a hopper 12 to be provided for use as molding material.
The glass fiber content in the final glass fiber reinforced thermoplastic resin molding material is preferably from 5 to 60 % by weight With a content less than % by weight, there is no remarkable effect of reinforcement with glass fibers On the other hand, a content exceeding 60 % by weight will make molding of the material difficult The amount of the resin to be coated by emulsion treatment is typically from 0 25 to 18 % by weight, while that by extrusion coating is typically from 94 75 to 22 % by weight.
The thermoplastic resin to be used for the aqueous emulsion in the first step and that for the extrusion coating may be the same or may be different resins compatible with each other These thermoplastic resins are generally selected from those as mentioned in Table 1 Preferable classes of combinations of these resins to be widely used in commercial application are set forth in Table 2 below.
TABLE 2
Oriented resin (formed Class by extrusion coating) Polystyrene (including rubber-modified highimpact polystyrene) 2 Acrylonitrile-styrene resin 3 Acrylonitrile-butadienestyrene resin; Methyl methacrylate-acrylonitrile-styrenebutadiene resin; Methyl methacrylate-styrenebutadiene resin; or Acrylonitrile-butadienea-methyl styrene-styrene resin 4 Polyphenylene ether or modified polyphenylene ether Polyethylene or polypropylene Non-oriented resin (formed from aqueous emulsion) Polystyrene resin or Styrene-butadiene resin Acrylonitrile-styrene resin; or a copolymer of styrene with at least one monomer selected from the group consisting of acrylonitrile, acrylic acid (derivative) and methacrylic acid (derivative) The same resin as in Class 2; or a resin of the same kind as the oriented resin Polyphenylene ether, modified polyphenylene ether or polystyrene resin Polyethylene, polypropylene, ethylenevinyl acetate copolymer or ethylene-methacrylic acid copolymer resin The thermoplastic resins as mentioned above to be used in the present invention have generally the melt-flow rates as shown in Table 3 below, which are measured by ISO-R 1133-1969 «Determination of the Melt Flow Rate of Thermoplastics» or a method similar thereto under conditions as given in the same Table.
1,592,310 TABLE 3
Thermoplastic resin Polystyrene Acrylonitrilestyrene MFR measurement conditions (temperature, load) C, 5 kg (procedure 8) 220 C, 10 kg ABS type resin PPE PE PP 220 C, 10 kg 250 C, 10 kg C, 2 16 kg (procedure 4) 230 C, 2 16 kg (procedure 12) In the following Table 4, there are shown the physical properties of the injection molded test pieces prepared from the molding material of the present invention utilizing AS resin as thermoplastic resin as obtained by the procedure as described in the following Example 1, as compared with those prepared by the methods of prior art, namely by blending chopped strands of glass fiber with molten
AS resin (reference example 1), by applying only emulsion coating of AS resin on glass fiber roving (reference example 2), by applying only extrusion coating of AS resin on glass fiber roving (reference example 3) and by first applying a solution coating of AS resin dissolved in methyl ethyl ketone on glass fiber roving, followed by extrusion coating of AS resin (reference example 4), using the same AS resins, respectively.
The range of MFR value 1-100 1-100 Remarks Rubber modified polystyrene being included Acrylonitrile/ styrene = 5/95-70/30 1-100 1-100 Modified PPE being included 0.03-100 0.1-100 1,592,310 R 9 1,592,310 9 TABLE 4
Reference Reference Reference Reference AS example example example example Example resin 1 2 3 4 1 Pre-treatment of glass fiber Glass fiber Content in pellet (%o; solvent separation method) Tensile strength (Kg/cm 2; JIS K 6871) Elongation (%; JIS K 6871) Flexural strength (Kg/cm 2; ASTM D 790) Flexural modulus (Kg/cm 2; ASTM D 790) None 730 1070 35000 None 1100 1500 70000 AS emulsion treatment alone 1100 1400 62000 None 800 1400 60000 AS 20 % MEK solution 850 AS emulsion treatment 1200 1300 55000 1640 73000 Izod impact strength (Kg cm/cm; JIS K 6871) Heat distortion temperature (C; JIS K 6871) Dispersion of glass fibers (visible observation of injection molded plate) 1.5 5.0 5-13 7 (greatly fluctuated) good bad Average glass fiber length in the molded article (microscopic observation of glass fibers separated by solvent) unmeasurable due 0.4 mm 0 75 mm to the presence of glass fiber balls 5-11 (greatly fluctuated) bad (insufficient glass fiber dispersion) 102 good unmeasurable due to the presence of glass fiber balls 1.2 mm 1,592,310 10 TABLE 4 (cont’d) Reference Reference Reference Reference AS example example example example Example resin 1 2 3 4 1 Abrasion of injection molding machine (visible None abraded abraded None observation after half year operation) As is apparent seen from Table 4, the glass fiber reinforced thermoplastic resin molding composition of the present invention can produce injection molded articles having excellent physical properties, being superior over commercially available glass fiber reinforced AS resin (reference example 1) in impact strength 5 (Izod impact strength) by as much as twice, and also remarkably in heatresistance (heat distortion temperature) Furthermore, creep characteristics at a high temperature are also found to be extremely improved It is believed that such improve-ments in physical properties can be ascribed to uniform dispersion of glass fiber filaments and longer average glass fiber length in the thermoplastic resin of the 10 injection molded article produced from the pellet of the present invention.
Furthermore, the injection molded article prepared from the present molding material has physical properties superior to those prepared from any other material known in the art, and the injection molding machine can be free from abrasion by use of the molding material of the present invention 15 The present invention is further illustrated by the following Examples and Comparison example.
Example 1.
Four bundles of glass fibers ( 2000 ends, 13 puo filaments in one bundle) are immersed in a AS resin (AN = 25 %, M F R = 5 g/10 min) emulsion with 50 solid 20 components The bundles subjected to coating treatment with said emulsion are dried under an atmosphere at 200 ‘C After drying, the AS resin coated roving contains 80 parts by weight of glass fibers and 20 parts by weight of AS resin.
AS resin is extruded through an extruder maintained at a barrel temperature of 160 to 180 ‘C on the hopper side and 200 to 2201 C on the outflowing side and a die 25 temperature of 2200 C at the rate of 12 kg/hour and supplied to the die Winding speed of the emulsion treated glass fiber bundle obtained above is controlled at 20 m/min, with the diameter of the extrusion coated strand being 3 8 mm) and only one strand being wound up This strand is cut into pellets with 3 5 mm length by a pelletizer The pellet obtained contains 20 wt % O of glass fibers, 4 wt % of non 30 oriented AS resin and 76 wt % of oriented AS resin The degree of orientation of the oriented AS resin is measured at 1600 C by the method as described above to be 1 % shrinkage The pellet can be readily broken with pincers to be separated into broken pieces of oriented resin and broken pieces of non-oriented resin containing glass fibers This pellet is molded by conventional injection molding to obtain an 35 article having physical properties as shown in Table 4 In addition to the excellent physical properties as mentioned above, the dispersion of the glass fibers in the molded article is found to be good without agglomeration (balls) of glass fibers.
Further, comparison is made about the melt flow property between the AS resin obtained by salting out the AS emulsion used in this Example and the AS resin 40 supplied from the extruder That is, melt flow properties of these resins are measured by, for example, Melt Flow Rate measuring device as determined in ISO RI 133 under the condition of 2200 C, 10 Kg load to give the same result of 5 g/10 min.
Example 2.
Example I is repeated using an AS resin emulsion of which AS resin after salting out has a melt flow rate of 10 g/10 min and an AS resin with a melt flow rate of 5 g/10 min to be supplied from the extruder, under otherwise the same conditions as in Example 1, to prepare a pellet with strand diameter of 3 8 mm) and 5 length of 3 5 mm By injection molding the resultant pellet by conventional method, there is obtained a molded article which is better in uniformity of the glass fibers dispersed in the molded article as well as surface appearance improved in flatness and gloss The melt flow property (injection molding pressure) is also slightly (by about 10 % decrease) improved As to the physical properties, Izod 10 impact strength is slightly improved to be 13 kg-cm/cm as compared with Example I, other properties being comparable to those of Example 1.
Example 3.
Four bundles of a glass fiber ( 2000 ends, 15 go mono-filaments in one bundle) are immersed in a styrene-butadiene resin (St/Bd = 6/4) emulsion (solid 15 components: 45 %) and dried at 1100 C The emulsion coated bundles after drying contains 85 parts by weight of glass fibers and 15 parts by weight of styrenebutadiene resin A polystyrene resin is extruded through an extruder maintained at a barrel temperature of 160 to 1800 C on the hopper side and 200 to 2200 C on the outlet side and a die temperature of 2200 C and supplied to an extrusion coating die 20 The glass fiber is wound up at a speed of 5 m/min with extruded strand diameter being 3 2 mmo Said strand is cut into pellets of 5 mm length Said pellets contain 30 wt.% O of the glass fibers, 5 3 wt % of non-oriented SB resin and 64 7 wt % O of oriented PS resin When injection molding of the pellets is performed by conventional method, the dispersion of the glass fibers is found to be good to give 25 an injection molded article having improved physical properties The styrenebutadiene resin used in this Example has a melt flow rate of 10 g/10 min and the polystyrene of 3 g/10 min (measured under the conditions of ISO-RI 133, procedure 8).
Example 4 30
Three bundles of glass fiber (each bundle comprising 2000 ends, filaments with diameters of 13 u) are immersed in an aqueous polystyrene resin emulsion with solid content of 40 % to apply coating treatment on each roving, followed by drying in an atmosphere maintained at 2000 C The composition of the roving coated with polystyrene resin after drying consists of 85 parts by weight of glass fiber and 15 35 parts by weight of polystyrene resin A mixture of polyphenylene ether resin and polystyrene resin (PPE/PS = 4/6, M F R = 7 g/10 min) is extruded through an extruder at cylinder temperature and die temperature of 2700 C, respectively at the rate of 75 kg/hour to be fed into the die On the other hand, winding speed of the glass fiber roving as prepared above is controlled at 20 m/minute with diameter of 40 extrusion coated strand of 3 2 mm, five strands being wound up at one time The resultant strand is cut into pellets by a pelletizer Glass fiber content in this pellet is found to be 20 wt % This pellet is injection molded by conventional method to obtain a molded article having Izod impact strength of 20 kg cm/cm and a heat distortion temperature of 145 C For comparative purpose, there are prepared 45 pellets of a mixture of the polyphenylene ether mixture with 20 % of glass fiber prepared by blending glass fiber with the polyphenylene ether mixture in an extruder, both being of the same kind as used in the above Example The pellets are similarly injection molded to obtain an article having an Izod impact strength of 10 kg cm/cm and a heat distortion temperature of 1400 C From this comparison, the 50 improved effect of the present invention can be seen and the glass fibers in the molded article of the present invention are found to be well dispersed therein without agglomeration (balls) of glass fibers, exhibiting a good appearance.
Example 5.
Example 1 is repeated except that an aqueous emulsion (solid: 50 %) of 55 ethylene-vinyl acetate copolymer (vinyl acetate: 28 %) is used in place of the AS emulsion, and a high density polyethylene (density = 0 950, MI = 3 g/10 min) in place of the AS resin for the extrusion coated outer covering layer resin The resultant molding material produces a molded article improved in mechanical properties to the same extent as observed in Example 1 60 l l I 1,592,310 1 1 Comparison Example.
In substantially the same step as in Example 1, in place of the AS resin emulsion, there is prepared a 20 wt % AS resin solution by dissolving an AS resin with substantially the same molecular weight as that contained in the AS emulsion in methyl ethyl ketone The same glass roving as used in Example 1 is immersed in 5 said AS resin solution, followed by drying The roving after drying contains 20 % by weight of AS resin adhered thereon Under the same conditions as in Example 1, the AS resin is extrusion coated on this roving to a final glass fiber content of 20 %/ by weight, followed by pelletizing The pellets obtained are injection molded to obtain an injection molded article, in which glass fibers are insufficiently dispersed 10 The injection molded articles have various fluctuations in physical properties, especially Izod impact strength While there may be considered various factors which will affect physical properties of the molded product such as viscosity of the AS resin methyl ethyl ketone solution, penetration degree of the resin solution into the roving and balance in amounts of the coating or adhesion of the resin on the 15 roving, it is believed that the insufficient dispersion of the glass fibers in the final molded product is ascribable to still insufficient affinity between the glass fibers and methyl ethyl ketone due to which no complete coating can be applied previously on the glass fibers.
As described above, the molding material of the glass fiber reinforced thermo 20 plastic resin of the present invention is a molding material which is very excellent in glass fiber reinforcing effect For molding the material of the present invention, there can be used various molding machines known in the art such as injection molding machine or an extruder and the material can be used as it is when applying these machines Due to uniform dispersion of the glass fibers in the material of the 25 present invention, it can produce molded articles with excellent physical properties and surface appearance of good smoothness and gloss Furthermore, the oriented outer resin is readily broken in a molding machine and the non-oriented resin present as thin film layer around glass fibers (an easily be molten to effect lubricating action between glass fibers and metals in molding machines, whereby 30 abrasion of machines is very small Thus, a variety of uses will be expected of the material provided by the present invention.

Claims (16)

WHAT WE CLAIM IS:-

1 A molding material which comprises ( 1) at least one inner rod-shaped body, each comprising a bundle of glass fiber filaments and a non-oriented thermoplastic 35 resin, said glass fiber filaments being respectively separated from each other and extending in parallel to each other through the said non-oriented resin and ( 2) an outer covering layer of an oriented thermoplastic resin which is substantially oriented in the axial direction of said glass fiber filaments and compatible with said non-oriented thermoplastic resin in the inner rod-shaped body 40

2 A molding material as claimed in claim 1, wherein the glass fiber content in the composition is from 5 to 60 % by weight, the proportion of the thermoplastic resin in the inner rod(s) is from 0 25 to 18 % by weight and that in the outer layer is from 94 75 to 22 % by weight, each being based on the total composition.

3 A molding material as claimed in claim 1 or 2, wherein the thermoplastic 45 resin for the outer layer is polystyrene or rubber-modified high-impact polystyrene and that for the inner rod(s) is polystyrene or styrene-butadiene copolymer.

4 A molding material as’claimed in claim I or 2, wherein the thermoplastic resin for the outer layer is acrylonitrile-styrene copolymer and that for the inner rod(s) is acrylonitrile-styrene copolymer or copolymers of styrene with at least one 50 monomer selected from acrylonitrile, acrylic acid and its derivatives, and methacrylic acid and its derivatives.

A molding material as claimed in claim I or 2, wherein the thermoplastic resin tfor the outer’layer’is selected from acrylonitrile-butadienestyrene copolymer, methyl methacrylate-acrylonitrile-styrene-butadiene copolymer, methyl meth 55 acrylate-styrene-butadiene copolymer and acrylonitrile-butadiene-a-methyl styrene copolymer and that for the inner rod(s) from acrylonitrilebutadienestyrene copolymer, methyl methacrylate-acrylonitrile-styrene-butadiene copolymer, methyl methacrylate-styrene-butadiene copolymer, acrylonitrilebutadiene-a-methyl styrene-styrene copolymer, acrylonitrile-styrene copolymer, and 60 copolymers of styrene with at least one monomer selected from acrylonitrile, acrylic acid and its derivatives, and methacrylic acid and its derivatives.

6 A molding material as claimed in claim 1 or 2, wherein the thermoplastic resin for the outer layer is polyphenylene ether or modified polyphenylene ether 1,592,310 and that for the inner rod(s) is polyphenylene ether, modified polyphenylene ether or polystyrene.

7 A molding material as claimed in claim I or 2, wherein the thermoplastic resin for the outer layer is polyethylene or polypropylene and that for the inner rod(s) is selected from polyethylene, polypropylene, ethylenevinyl acetate 5 copolymer and ethylenic ionomer.

8 A molding material as claimed in any -one of claims I to 8, wherein the thermoplastic resin for the outer layer and that for the inner rod(s) are of the same polymer.

9 A molding material as claimed in any one of claims I to 9, wherein the

10 thermoplastic resin for the outer layer has a melt flow rate not higher than that for the inner rod(s).
A molding material as claimed in claim I substantially as described herein with reference to Figs I to 3 of the accompanying drawings.

11 A molding material as claimed in claim 1 substantially as described in any 15 one of the Examples.

12 A process for the preparation of a molding material as claimed in Claim I which comprises first treating at least one glass fiber roving comprising from 500 to 20000 end filaments with an aqueous emulsion of a thermoplastic resin to disperse each filament uniformly in said emulsion, followed by drying, to form an inner 20 thermoplastic resin rod containing the glass fiber monofilaments extending therethrough in parallel to each other separated by the thus formed nonoriented, thin interseptal resin and then extrusion coating on to one or more thus formed inner rod(s) another thermoplastic resin which is compatible with the thermoplastic resin of the inner rod to form an outer covering layer oriented in the direction of 25 extrusion on the non-oriented inner resin rod(s), and pelletizing the coated product into a suitable size of pellets.

13 A process as claimed in Claim 13 substantially as described herein with reference to Figs 5 and 6 of the accompanying drawings.

14 A process as claimed in claim 13 substantially as described in any one of 30 the Examples.

A molded article produced from a molding material as claimed in any one of claims 1 to 11.

16 A molded article produced from a molding material prepared by a process as claimed in any one of claims 12 to 14 35 BROOKES & MARTIN, High Holborn House, 52/54 High Holborn, London, WCIV 65 E, Agents for the Applicants.
Printed for Her Majesty’s Stationery Office by the Courier Press, Leamington Spa, 1981.
Published by the Patent Office, 25 Southampton Buildings, London, WOZA l AY, from which copies may be obtained.
I 1,592,310

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Glass fibre reinforced thermoplastic resin moulding material

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(en)

Families Citing this family (51)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

GB2067612A
(en)

1980-01-23
1981-07-30
Smith H R
Fibre reinforced materials and methods of making and using them

DE3041021A1
(en)

1980-10-31
1982-06-09
Artur 5221 Hermesdorf Rudolf

FIBER REINFORCED PLASTIC MOLDING

DE3280480T2
(en)

1981-01-21
1999-11-11
Kawasaki Chem Holding

Granules made of fiber-reinforced composites and their manufacturing processes

FR2576247B1
(en)

1985-01-18
1987-07-31
Michelin & Cie

REINFORCING ASSEMBLIES COMPRISING REINFORCEMENT THREADS AND A MATRIX; PROCESS FOR OBTAINING SUCH ASSEMBLIES; ARTICLES COMPRISING SUCH PACKAGES

DE3606473A1
(en)

1986-02-28
1987-09-03
Huels Chemische Werke Ag

COMPONENTS MADE OF POLYPHENYLENE ETHERS AND ELASTOMERIC, THERMOPLASTICALLY PROCESSABLE STYLENE-CONTAINING BLOCK COPOLYMERS, AND METHOD FOR THE PRODUCTION THEREOF

US4960642A
(en)

1986-04-17
1990-10-02
The Furukawa Electric Co., Ltd.
Pellets for making electromagnetic wave shielding material and method for manufacturing the same

WO1987006178A1
(en)

1986-04-17
1987-10-22
The Furukawa Electric Co., Ltd.
Pellet of electromagnetic wave shielding material and producing thereof

DE3615965A1
(en)

1986-05-13
1987-11-19
Huels Chemische Werke Ag

COMPONENTS MADE OF FIBER-SHAPED STRENGTHENERS AND RUBBER AND METHOD FOR THEIR PRODUCTION

US4818615A
(en)

1986-06-02
1989-04-04
American Cyanamid Company
Elongated molding granules and injection-molding process employing them

FR2600585B1
(en)

1986-06-30
1988-11-10
Galichon Jean

PROCESS FOR THE MANUFACTURE OF THERMOSTABLE PARTS IN COMPOSITE MATERIALS AND THE PARTS OBTAINED THEREBY

US4808481A
(en)

1986-10-31
1989-02-28
American Cyanamid Company
Injection molding granules comprising copper coated fibers

DE3638189A1
(en)

1986-11-08
1988-05-11
Wolff Walsrode Ag

METHOD AND DEVICE FOR APPLYING AND IMPROVING FLEECE MATERIALS WITH VISCOSIC LIQUIDS

BE1000277A3
(en)

1987-01-30
1988-10-04
Bekaert Sa Nv
COMPOSITE GRANULATE crimped fibers COMPREHENSIVE AND PLASTIC ITEMS MANUFACTURED THEREFROM.

US4775591A
(en)

1987-06-01
1988-10-04
General Electric Company
Ionomer compositions and method for their preparation

EP0306671A1
(en)

1987-07-20
1989-03-15
Hitachi, Ltd.
Electroconductive resin composition for moulding, and shield moulded therefrom

US4880674A
(en)

1987-10-19
1989-11-14
Katayama Kogyo Co., Ltd.
Synthetic resin molding for automotive vehicles

FR2625276B1
(en)

1987-12-23
1993-10-22
Vibrachoc

REINFORCEMENT AND DAMPING FILAMENT, AND DAMPING ELEMENT OBTAINED BY ARRANGING A PLURALITY OF FILAMENTS

DK8289A
(en)

1988-01-12
1989-07-13
Raychem Ltd

COMPOSITE

DE3806661A1
(en)

1988-03-02
1989-09-14
Kabelmetal Electro Gmbh

METHOD FOR PRODUCING PLASTIC-REINFORCED OBJECTS FROM PLASTIC

EP0360430B1
(en)

1988-09-20
1995-06-14
MITSUI TOATSU CHEMICALS, Inc.
Molding material

CA2001142C
(en)

1988-10-21
2000-09-05
Tatsuki Matsuo
Molding material for thermoplastic composites

US5091255A
(en)

1990-01-23
1992-02-25
American Cyanamid Company
Molding granules, their manufacture and their use in the production of molded articles

US5340520A
(en)

1992-06-10
1994-08-23
Beech Aircraft Corp.
Non-woven mat surface ply for woven fabric

DE9302401U1
(en)

1993-02-19
1993-06-17
Hoechst Ag, 6230 Frankfurt, De

DE4326232A1
(en)

1993-08-05
1995-02-09
Roehm Gmbh

Plastic composites made of incompatible plastics

US5763042A
(en)

1994-06-28
1998-06-09
Reichhold Chemicals, Inc.
Reinforcing structural rebar and method of making the same

US5500175A
(en)

1994-11-02
1996-03-19
Bradt; Rexford H.
Process of producing heat-softenable, hopper-feedable plastic pellets containing folded reinforcing fibers

JPH08183030A
(en)

1994-12-28
1996-07-16
Daicel Chem Ind Ltd
Long fiber reinforced impact-resistant polystyrene resin structure and molded product thereof

GB9615995D0
(en)

1996-07-30
1996-09-11
Kobe Steel Europ Ltd
Fibre reinforced compositions and methods for their production

US6533882B1
(en)

1996-08-12
2003-03-18
Owens Corning Fiberglas Technology, Inc.
Chemical treatments for fibers and wire-coated composite strands for molding fiber-reinforced thermoplastic composite articles

AU765900B2
(en)

1996-08-12
2003-10-02
Owens Corning
Chemical treatments for fibers and wire-coated composite strands for molding fiber-reinforced thermoplastic composite articles

AU733283B2
(en)

1996-08-12
2001-05-10
Owens Corning
Chemical treatments for fibers and wire-coated composite strands for molding fiber-reinforced thermoplastic composite articles

US6099910A
(en)

1996-08-12
2000-08-08
Owens Fiberglas Technology, Inc.
Chemical treatments for fibers

US5789477A
(en)

1996-08-30
1998-08-04
Rutgers, The State University
Composite building materials from recyclable waste

US6258453B1
(en)

1996-09-19
2001-07-10
Lawrence V. Montsinger
Thermoplastic composite materials made by rotational shear

EP0929394B1
(en)

1996-10-07
2002-01-30
Marshall Industries Composites
Reinforced composite product and apparatus and method for producing same

SE511439C2
(en)

1997-06-16
1999-09-27
Amal Ab

Method for providing a bending stiff, elongated body and a device for a bending stiff, elongated body

JPH1135701A
(en)

1997-07-15
1999-02-09
Sumitomo Chem Co Ltd
Fiber-reinforced thermoplastic resin molding

US6103295A
(en)

1997-12-22
2000-08-15
Mds Nordion Inc.
Method of affixing radioisotopes onto the surface of a device

US6394945B1
(en)

1997-12-22
2002-05-28
Mds (Canada), Inc.
Radioactively coated devices

US6162536A
(en)

1999-02-10
2000-12-19
Montsinger; Lawrence V.
Conductive long fiber polyvinyl chloride composites

US20020187346A1
(en)

2001-06-04
2002-12-12
Adzima Leonard J.
Powder coated roving for making structural composite

US7628745B2
(en)

2001-12-19
2009-12-08
Gallus Ferd. Ruesch Ag
Pressure cylinder in the form of a hollow cylinder made of metal

FR2882958B1
(en)

2005-03-09
2011-03-18
Saint Gobain Vetrotex

CONCENTRATED REINFORCING STICKS AND THEIR MANUFACTURE

WO2007129624A1
(en)

2006-05-01
2007-11-15
Nippon Sheet Glass Company, Limited
Reinforcing cord, method for producing the same, and product using the reinforcing cord

US8206526B2
(en)

2008-08-20
2012-06-26
Claude Baril
Process for reducing wrinkles in composite laminated structures

JP5286227B2
(en)

2009-11-06
2013-09-11
株式会社神戸製鋼所

Method for connecting reinforcing fiber bundles, method for producing long fiber reinforced thermoplastic resin pellets, and wound body

CN102230247A
(en)

2011-06-20
2011-11-02
昆山维信纺织工业有限公司
Yarn

EP3068600B1
(en)

2013-11-15
2020-02-19
SABIC Global Technologies B.V.
Process for producing a glass fibre-reinforced thermoplastic polymer composition

DE102016104071B4
(en)

2016-03-07
2018-10-25
Groz-Beckert Kg

Method for bending a reinforcing bar of a reinforcing element and bending device

JP7081335B2
(en)

2018-03-15
2022-06-07
株式会社リコー

Manufacturing equipment for 3D objects and manufacturing method for 3D objects

Family Cites Families (8)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US2877501A
(en)

1952-12-24
1959-03-17
Fiberfil Corp
Glass-reinforced thermoplastic injection molding compound and injection-molding process employing it

GB1116923A
(en)

1964-08-20
1968-06-12
British Ropes Ltd
Improvements in or relating to ropes, strands and cores

US3608033A
(en)

1969-06-17
1971-09-21
Liquid Nitrogen Processing
Process for production of molding compositions containing high weight percentage of glass

US3671384A
(en)

1969-11-04
1972-06-20
Monsanto Co
Glass concentrate capsules

US3671378A
(en)

1969-11-04
1972-06-20
Monsanto Co
Glass fiber reinforced composite and method of making same

US3660974A
(en)

1970-08-31
1972-05-09
Owens Corning Fiberglass Corp
Industrial belt construction

US4037011A
(en)

1972-02-15
1977-07-19
Dart Industries Inc.
Glass fiber reinforced thermoplastic composition and process for its preparation

JPS5143501B2
(en)

1973-01-27
1976-11-22

1978

1978-04-13
US
US05/896,433
patent/US4169186A/en
not_active
Expired – Lifetime

1978-04-13
GB
GB14593/78A
patent/GB1592310A/en
not_active
Expired

1978-04-17
FR
FR7811248A
patent/FR2423320A1/en
active
Granted

1978-04-19
NL
NLAANVRAGE7804183,A
patent/NL171550C/en
not_active
IP Right Cessation

Also Published As

Publication number
Publication date

NL171550C
(en)

1983-04-18

NL171550B
(en)

1982-11-16

US4169186A
(en)

1979-09-25

NL7804183A
(en)

1979-10-23

FR2423320A1
(en)

1979-11-16

FR2423320B1
(en)

1980-09-26

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