CA1108817A - Molding material structure - Google Patents
Molding material structureInfo
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- CA1108817A CA1108817A CA301,396A CA301396A CA1108817A CA 1108817 A CA1108817 A CA 1108817A CA 301396 A CA301396 A CA 301396A CA 1108817 A CA1108817 A CA 1108817A
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- resin
- thermoplastic resin
- styrene
- molding material
- glass fiber
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Abstract
IMPROVED MOLDING MATERIAL STRUCTURE
Abstract of the disclosure:
A molding material structure of a thermoplastic resin composition comprising (1) at least one pillar-shaped body made of a bundle of glass fiber filaments and a non-oriented thermoplastic resin and (2) an outer covering layer of an oriented thermoplastic resin compatible with the resin in said inner body is found to produce molded articles in which glass fiber filaments are dispersed uniformly in the resin matrix with longer average length to improve various properties of molded articles, especially impact strength.
Abstract of the disclosure:
A molding material structure of a thermoplastic resin composition comprising (1) at least one pillar-shaped body made of a bundle of glass fiber filaments and a non-oriented thermoplastic resin and (2) an outer covering layer of an oriented thermoplastic resin compatible with the resin in said inner body is found to produce molded articles in which glass fiber filaments are dispersed uniformly in the resin matrix with longer average length to improve various properties of molded articles, especially impact strength.
Description
p~
This invention relates to an impro~ed molding material structure of a 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 to improve various properties of molded articlesg said structure being also improved in processing characteristics and free from such problems as damaging molding machines through frictional abrasion with the glass fibers contained therein.
Molded articles of glass flber reinforced thermo-p:Lastic resins have been used as useful moldin~ materials having excellent physical properties, especla].ly mechanical strength, as well as excellent moldability inherent in thermoplastic resins. Since oil shock in 19739 they have further arrested attention as utili-zation of the material with higher added value and improvement of their physlcal properties has been keenly longed for. In prior art9 these molded articles have been prepared especially by injection molding f`rom various molding materials. Among them, typical commercially available injection molding material for glass iber reinforced thermoplastic products is constituted of chopped strands of a glass fiber dispersed in a thermoplastic resin9 which is prepared by extrusion of a thermoplastic resin together with glass fibers.
Alternatively, another type of molding material havlng glass fiber core enclosed within a thermoplastic resin as outer coating or shell is also known in the art9 as disclosed by U.S. Patent 29877~501 and U.S. Patent 3,608~033. The molding material of the former type, 8~
while it is advantageous in simple and easy preparation procedure 7 it is entirely impossible to have mono-filaments with longer lengths dispersed uniformly throughout the resin. Thus~ this type of molding material can enjoy only limited reinforcing effect with glass fibers inherent within such a structure. On the other hand, in the latter type of molding materia].g 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 uniforml,y dispersed in the resin when fabrlcated into a molded article. ~urthermore, with such a uni-layer coverage of ~glass fibers~ the molding material cannot be free from the problem of damaging mechanical parts at the time of molding because glass fibers exposed by disintegration of outer shell are directly contacted with such mechanical parts.
It is an object of the present invention to provide a molding material of Klass fiber reinforced thermoplastic resin which will not cause damaging of molding machines through frictional abrasion and can be molded into an article in which glass fibers with longer length are dispersed uniformly to improve reinforcing characteristics of the thermoplastic resin.
Another object of the present invention is to provide a process for producing a molding material of glass fiber reinforced thermoplastic resin as mentioned above by a simple and safe as well as economical procedure.
Still another object of the present invention 8~L~
is to prov.ide a molded ar-ticle of glass fiber reinforced thermoplastic resin improved in physical properties, especially mechanical streng-th.
According to the present invention, there is provided a molding material structure w:hich comprises (1) at least one inner pillar-shaped body, each comprising a bundle of glass fiber filaments and a non-orien-ted thermoplastic resin, the glass fiber being respectively separated Erom each other and extending in parallel to each other through the said non-oriented resin and (2) an outer cove.ring layer of an oriented thermop:l.asti.c res:i.n which is suhstant:ia:l.:Ly oriented in the axial direction of the glass fiber filaments and compatible with the non-oriented thermoplastic resin in the inner pillar-shaped body wherein glass fiber content in the composition is from 5 .to 60 % by weight, the proportion oE the thermoplastic resin in the inner body from 0.25 to 18 %
by weight and that in the outer layer from 9~.75 to 22 % by weight, each being based on the total composition arl~ the ~o length of the structure is from 1~~ mm.
The improved molding material structure o:E the present invention may be bet-ter understood with reference to the acccompanying drawings, in which:
Fig. 1 shows cross-sectional view in the vertical direction of one embodiment of the present invention shaped in right cyl.indrical pellet, in whi.ch there are five inner bodies of a thermoplastic resin containing glass fiber filaments embedded in an outer covering layer of thermoplas-tic resin;
dm~
Fig. 2 perspective, partially exploded view of the right cylindrical pellet, of which vertical cross-sectional view is shown in Fig. 1, taken along the line A-A in Fig. 1, showing only the ou-ter covering resin layer portion from which the inner resin bodies containing glass fiber filaments are plucked out;
""~ ~ , ,J~' (1rn ~
Fig. 3 perspective view of the lnner resin body plucked out from the right cylindrical pellet as shown in Flgs. l and 2j Fig. 4 schematic illustrat;ions of the structures of prior art9 indicating the states of fracture thereof;
Figo 5 a flow sheet a illustrative schematically of the steps of the process for preparation of the molding material structure of the present inventionj and Fig 6 a longitudinal cross-sectional view of one example of a die to be used for preparation of the molding material structure of the present invention.
~ s shown in ~ . 1, at least one inner res:ln body 2 containlng a large number of mono-filaments 3 are embedded in outer covering resin layer l. In one aspect~
the inner thermoplastic resin body in the present molding material structure is required to be non-oriented~ while the outer covering thermoplastic resin layer substantially oriented. The terms "non-oriented" and "substantially oriented" herein used mean whether there is substantial shrinkage of the resin in a certain direction when measured under conditions as hereinafter specified.
The inner thermoplastic resin body 2 of the present structure contains a large number of mono-filaments which extend in parallel to each other through
This invention relates to an impro~ed molding material structure of a 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 to improve various properties of molded articlesg said structure being also improved in processing characteristics and free from such problems as damaging molding machines through frictional abrasion with the glass fibers contained therein.
Molded articles of glass flber reinforced thermo-p:Lastic resins have been used as useful moldin~ materials having excellent physical properties, especla].ly mechanical strength, as well as excellent moldability inherent in thermoplastic resins. Since oil shock in 19739 they have further arrested attention as utili-zation of the material with higher added value and improvement of their physlcal properties has been keenly longed for. In prior art9 these molded articles have been prepared especially by injection molding f`rom various molding materials. Among them, typical commercially available injection molding material for glass iber reinforced thermoplastic products is constituted of chopped strands of a glass fiber dispersed in a thermoplastic resin9 which is prepared by extrusion of a thermoplastic resin together with glass fibers.
Alternatively, another type of molding material havlng glass fiber core enclosed within a thermoplastic resin as outer coating or shell is also known in the art9 as disclosed by U.S. Patent 29877~501 and U.S. Patent 3,608~033. The molding material of the former type, 8~
while it is advantageous in simple and easy preparation procedure 7 it is entirely impossible to have mono-filaments with longer lengths dispersed uniformly throughout the resin. Thus~ this type of molding material can enjoy only limited reinforcing effect with glass fibers inherent within such a structure. On the other hand, in the latter type of molding materia].g 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 uniforml,y dispersed in the resin when fabrlcated into a molded article. ~urthermore, with such a uni-layer coverage of ~glass fibers~ the molding material cannot be free from the problem of damaging mechanical parts at the time of molding because glass fibers exposed by disintegration of outer shell are directly contacted with such mechanical parts.
It is an object of the present invention to provide a molding material of Klass fiber reinforced thermoplastic resin which will not cause damaging of molding machines through frictional abrasion and can be molded into an article in which glass fibers with longer length are dispersed uniformly to improve reinforcing characteristics of the thermoplastic resin.
Another object of the present invention is to provide a process for producing a molding material of glass fiber reinforced thermoplastic resin as mentioned above by a simple and safe as well as economical procedure.
Still another object of the present invention 8~L~
is to prov.ide a molded ar-ticle of glass fiber reinforced thermoplastic resin improved in physical properties, especially mechanical streng-th.
According to the present invention, there is provided a molding material structure w:hich comprises (1) at least one inner pillar-shaped body, each comprising a bundle of glass fiber filaments and a non-orien-ted thermoplastic resin, the glass fiber being respectively separated Erom each other and extending in parallel to each other through the said non-oriented resin and (2) an outer cove.ring layer of an oriented thermop:l.asti.c res:i.n which is suhstant:ia:l.:Ly oriented in the axial direction of the glass fiber filaments and compatible with the non-oriented thermoplastic resin in the inner pillar-shaped body wherein glass fiber content in the composition is from 5 .to 60 % by weight, the proportion oE the thermoplastic resin in the inner body from 0.25 to 18 %
by weight and that in the outer layer from 9~.75 to 22 % by weight, each being based on the total composition arl~ the ~o length of the structure is from 1~~ mm.
The improved molding material structure o:E the present invention may be bet-ter understood with reference to the acccompanying drawings, in which:
Fig. 1 shows cross-sectional view in the vertical direction of one embodiment of the present invention shaped in right cyl.indrical pellet, in whi.ch there are five inner bodies of a thermoplastic resin containing glass fiber filaments embedded in an outer covering layer of thermoplas-tic resin;
dm~
Fig. 2 perspective, partially exploded view of the right cylindrical pellet, of which vertical cross-sectional view is shown in Fig. 1, taken along the line A-A in Fig. 1, showing only the ou-ter covering resin layer portion from which the inner resin bodies containing glass fiber filaments are plucked out;
""~ ~ , ,J~' (1rn ~
Fig. 3 perspective view of the lnner resin body plucked out from the right cylindrical pellet as shown in Flgs. l and 2j Fig. 4 schematic illustrat;ions of the structures of prior art9 indicating the states of fracture thereof;
Figo 5 a flow sheet a illustrative schematically of the steps of the process for preparation of the molding material structure of the present inventionj and Fig 6 a longitudinal cross-sectional view of one example of a die to be used for preparation of the molding material structure of the present invention.
~ s shown in ~ . 1, at least one inner res:ln body 2 containlng a large number of mono-filaments 3 are embedded in outer covering resin layer l. In one aspect~
the inner thermoplastic resin body in the present molding material structure is required to be non-oriented~ while the outer covering thermoplastic resin layer substantially oriented. The terms "non-oriented" and "substantially oriented" herein used mean whether there is substantial shrinkage of the resin in a certain direction when measured under conditions as hereinafter specified.
The inner thermoplastic resin body 2 of the present structure contains a large number of mono-filaments which extend in parallel to each other through
2~ the resin body in the longitudinal direction thereof7 as shown in ~i~. 3. The resin in the inner body 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 lengthO Such a structure of the inner body 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 un~formly dispersed in the resultant molded article. The filaments 3 ln the inner body 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 ~ to 20 microns. These glass rovings are usually treated with so called sizing compound, typically silicon type coupling agents, during manu-facturing steps of glass fibers. Most of the presently avallable ~lass ~iber rovlngs conta:ln about l wt.% of such a coupling agent, lubricant or sheafing agent.
The shape of the inner body 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 vertical cross--section is generally ellipsoidal or spherical, it may also be otherwise such as triangular, rectangular or multangular. The number of such inner bodies may be variable from l to 40 or even higher, preferably from 1 to 10 depending on various conditions in the intended uses or preparation methods, but it is most preferably from l to 5.
~5 mentioned aboveg the outer covering resin layer l of the present molding material structure is required to be substantially oriented in the axial direction of the glass fiber filaments contained in the inner resin body as described aboveO One of the advantage of the molding material structure of the present -- 6 ~
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 structure of the in~ention.
To speak of injection molding9 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 moldin~ machine but there occurs me:Lting of pellets simultaneously with fracture thereof. ~rictional abrasion of metals such as screw or barrel is considered ko be due to the friction with glass flber before the resin containing ~,lass fiber is molten. ~or example9 in case of the blended glass fiber composition of prior artg abrasion in the region from feed zone to compression zone is so great that after a month's operation the in~ection molding machine may sometimes fail to give favorable molded articles. In other words, at meltingg kneading and measuring portions of the screw wherein the 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 earlier melting of local sections of the thermoplastic resin around the glass fiber. Namely9 the outer covering resin layer which is oriented in the axial direction of glass fiber is liable to be readily broken in 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 khe oriented outer layer and the inner body containing glass fiber filaments enclosed within non-oriented thin layer resin (see Fig. 2 and Fig. 3).
Thusg the inner resin body containing glass fiber filaments is removed from the outer covering resin layer and therefore the thin resin portion around the glass fiber is directly heatedg without intermedi.ary poorly thermoconductive resin layerg in the screw to be readily moltenO In contrastg as shown in Fig. L~(a)g when the glass fiber is enclosed within only one non-oriented resin structure, it takes a long time before whole of a thick resin portion around the fiber is molten and therefore the machine suffers from frictional abrasion of screw or barrel1 furthermoreg the fibers are also broken together with the resing failing to give molded articles containing glass fibers with long average lengthO On the other hand, as shown in Fig. 4~b)g when a bundle of glass fiber filaments is enclosed only within an oriented resin, the glass fibers are 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 inventiong the glass fiber content in the inner thermoplastic resin body is from 5 to 60 % by weight based on the total compositiong the proportion of the non-oriented resin in the inner body from 0.25 to 18 % by weight and the proportion of the orienked resin in the outer covering resin layer from 94O75 to 22 % by weight~ each being based on the total composition.
~8E~7 In the present inventiong the thermoplastic resin to be used for the oriented outer covering resin layer is required to be compatible with the thermoplastic resin to be used for the non-oriented resin body. 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 layerg respectively, are set forth in the following Table 1:
_able 1 . _ __ ___ __ _ __ __ ___ __ PS AS ABS PPl~, PE PP POM PC PA PMMA PVC Ionomer 'PS---'''-'~- C __ _. __ __ _ __ _ _~ _.
AS N C _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .................... __I
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
. _ _ _ _ I . _ _ 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=compatibleg L=limitedly compatible, N=non-compatible~ PS=polystyrene(including high-impact poly-styrene)~ AS=acrylonitrile-styrene copolymer; ABS=acrylo-nitrile-butadiene-styrene copolymer(including methyl methacrylate-butadiene-styrene~ methyl methacrylate-acrylonitrile-butadiene styrene and acrylonitrile-butadiene-a-methyl-styrene-styrene copolymers) 3 PPE=
polyphenylene ether(including modified PPE)~ PE=poly-ethylene; PP-polypropylene; POM=polyoxymethy:Lene J PC=
polycarbonate; PA=polyamide; PMMA=polymethyl methacrylate PVC=polyvinyl chloride g .7 The 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 strengthg 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 quantitatively, howeverg the substantial orientation required for the outer thermoplastic resin layer is defined as having at least 0.5 % therma] shrinkage in the axial direction which is observed when the oriented resin, from which the non-oriented glass fiber containing inner layer has been removed, :Ls exposed to heat at a temperature higher by about Ll5C than the ~icat softening point (~STM-D-1525) of the oriented resin 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 body 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 required to have affinity with glass fiber and a low viscosity of 100 centi-poise or less.
~or this purpose9 it is preferred to use an aqueous emulsion having small particles of a thermoplastic resin dispersed in waterO When glass fiber roving is immersed in such an aqueous emulsion and dried, small particles of the resin are adhered around each mono-filament of the glass fiber. Such small particles of a thermoplastic resin will form, even when molten at a high temperature to be fused with each other~ a substantially non-orîented 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 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 structure of the present invention is not particularly limited in its shape but inclusive of all shapes and sizes known in the art as pellets. Preferably9 however, it is shaped in cylinders with spherical or ellipsoidal cross-sections vertical to the axial direction of the glass fibers contained therein with shorter diameters ranging from l mm to 8 mm and lon~er diameters ~an!~ing!~rom 1 m~ to 15 mm~ the 1ength of tk~cyl~n~e~s bqing preferably ~`r~rn l ~ to 2~ mm~l If desired, other shapes including cylinders with tri-angular, rectangular, multangular cross-sections may also be employed.
There may be employed various methods for preparation of the molding material structure 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. 5 and 6~
38~L7 the process ~or preparation of the present molding material structure is described in detail belowO The process of the present invention comprises first treating at least one g].ass 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 resin body containing the glass fiber mono-filaments extending therethrough in parallel to each other separated by the thus formed non-orientedg thin inter-septal resin and then applying extrusiorl coating on the thus formed inner layer of another thermoplastic r-esin which is compatlble with said thermoplastic resin ~or inner body to form an outer covering layer oriented in the direction of extrusion on said non-oriented inner resin body, and pelletizing the glass fiber roving enclosed within double structured layers into 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 wlth an emulsion of a thermoplastic resin which is compatible with the thermo-plastic resin to be used for extrusion coating. As mentioned above~ commercially available glass fiber roving generally employs a bundle of about 2,000 filamentsg each filament being in the order of about 10 micron3 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 ~hich is hydrophilic in nature previously with an aqueous resin emulsion which is low in viscosity9 each of the glass fiber ~ilaments 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 ~igo 5, glass fiber roving 4 is led into pre-treatment liquid bath 5 to 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 Ll while it is immersed in and passed through said liquid bath to thereby coating each element of glass fiber mono-filaments with the aqueous resin emulsion to be adhered thereon.
Immersion of the glass f'iber roving in said resin emulsion may simply be conducted by passing -through said resin emulsion which is contained in a conventional liquld bath. Alternatively, a vibrator such as ultra-sonic vibrator is provided in said emulsion liquid bath so as to vibrate the emulsion~ whereby the immersion effect(coating adhesion effect) can be complete and production speed can also be accelerated.
The amount o~ 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 resi,n content adhered after drying said emulsion9 preferably ]5 to 25
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 un~formly dispersed in the resultant molded article. The filaments 3 ln the inner body 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 ~ to 20 microns. These glass rovings are usually treated with so called sizing compound, typically silicon type coupling agents, during manu-facturing steps of glass fibers. Most of the presently avallable ~lass ~iber rovlngs conta:ln about l wt.% of such a coupling agent, lubricant or sheafing agent.
The shape of the inner body 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 vertical cross--section is generally ellipsoidal or spherical, it may also be otherwise such as triangular, rectangular or multangular. The number of such inner bodies may be variable from l to 40 or even higher, preferably from 1 to 10 depending on various conditions in the intended uses or preparation methods, but it is most preferably from l to 5.
~5 mentioned aboveg the outer covering resin layer l of the present molding material structure is required to be substantially oriented in the axial direction of the glass fiber filaments contained in the inner resin body as described aboveO One of the advantage of the molding material structure of the present -- 6 ~
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 structure of the in~ention.
To speak of injection molding9 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 moldin~ machine but there occurs me:Lting of pellets simultaneously with fracture thereof. ~rictional abrasion of metals such as screw or barrel is considered ko be due to the friction with glass flber before the resin containing ~,lass fiber is molten. ~or example9 in case of the blended glass fiber composition of prior artg abrasion in the region from feed zone to compression zone is so great that after a month's operation the in~ection molding machine may sometimes fail to give favorable molded articles. In other words, at meltingg kneading and measuring portions of the screw wherein the 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 earlier melting of local sections of the thermoplastic resin around the glass fiber. Namely9 the outer covering resin layer which is oriented in the axial direction of glass fiber is liable to be readily broken in 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 khe oriented outer layer and the inner body containing glass fiber filaments enclosed within non-oriented thin layer resin (see Fig. 2 and Fig. 3).
Thusg the inner resin body containing glass fiber filaments is removed from the outer covering resin layer and therefore the thin resin portion around the glass fiber is directly heatedg without intermedi.ary poorly thermoconductive resin layerg in the screw to be readily moltenO In contrastg as shown in Fig. L~(a)g when the glass fiber is enclosed within only one non-oriented resin structure, it takes a long time before whole of a thick resin portion around the fiber is molten and therefore the machine suffers from frictional abrasion of screw or barrel1 furthermoreg the fibers are also broken together with the resing failing to give molded articles containing glass fibers with long average lengthO On the other hand, as shown in Fig. 4~b)g when a bundle of glass fiber filaments is enclosed only within an oriented resin, the glass fibers are 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 inventiong the glass fiber content in the inner thermoplastic resin body is from 5 to 60 % by weight based on the total compositiong the proportion of the non-oriented resin in the inner body from 0.25 to 18 % by weight and the proportion of the orienked resin in the outer covering resin layer from 94O75 to 22 % by weight~ each being based on the total composition.
~8E~7 In the present inventiong the thermoplastic resin to be used for the oriented outer covering resin layer is required to be compatible with the thermoplastic resin to be used for the non-oriented resin body. 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 layerg respectively, are set forth in the following Table 1:
_able 1 . _ __ ___ __ _ __ __ ___ __ PS AS ABS PPl~, PE PP POM PC PA PMMA PVC Ionomer 'PS---'''-'~- C __ _. __ __ _ __ _ _~ _.
AS N C _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .................... __I
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
. _ _ _ _ I . _ _ 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=compatibleg L=limitedly compatible, N=non-compatible~ PS=polystyrene(including high-impact poly-styrene)~ AS=acrylonitrile-styrene copolymer; ABS=acrylo-nitrile-butadiene-styrene copolymer(including methyl methacrylate-butadiene-styrene~ methyl methacrylate-acrylonitrile-butadiene styrene and acrylonitrile-butadiene-a-methyl-styrene-styrene copolymers) 3 PPE=
polyphenylene ether(including modified PPE)~ PE=poly-ethylene; PP-polypropylene; POM=polyoxymethy:Lene J PC=
polycarbonate; PA=polyamide; PMMA=polymethyl methacrylate PVC=polyvinyl chloride g .7 The 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 strengthg 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 quantitatively, howeverg the substantial orientation required for the outer thermoplastic resin layer is defined as having at least 0.5 % therma] shrinkage in the axial direction which is observed when the oriented resin, from which the non-oriented glass fiber containing inner layer has been removed, :Ls exposed to heat at a temperature higher by about Ll5C than the ~icat softening point (~STM-D-1525) of the oriented resin 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 body 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 required to have affinity with glass fiber and a low viscosity of 100 centi-poise or less.
~or this purpose9 it is preferred to use an aqueous emulsion having small particles of a thermoplastic resin dispersed in waterO When glass fiber roving is immersed in such an aqueous emulsion and dried, small particles of the resin are adhered around each mono-filament of the glass fiber. Such small particles of a thermoplastic resin will form, even when molten at a high temperature to be fused with each other~ a substantially non-orîented 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 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 structure of the present invention is not particularly limited in its shape but inclusive of all shapes and sizes known in the art as pellets. Preferably9 however, it is shaped in cylinders with spherical or ellipsoidal cross-sections vertical to the axial direction of the glass fibers contained therein with shorter diameters ranging from l mm to 8 mm and lon~er diameters ~an!~ing!~rom 1 m~ to 15 mm~ the 1ength of tk~cyl~n~e~s bqing preferably ~`r~rn l ~ to 2~ mm~l If desired, other shapes including cylinders with tri-angular, rectangular, multangular cross-sections may also be employed.
There may be employed various methods for preparation of the molding material structure 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. 5 and 6~
38~L7 the process ~or preparation of the present molding material structure is described in detail belowO The process of the present invention comprises first treating at least one g].ass 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 resin body containing the glass fiber mono-filaments extending therethrough in parallel to each other separated by the thus formed non-orientedg thin inter-septal resin and then applying extrusiorl coating on the thus formed inner layer of another thermoplastic r-esin which is compatlble with said thermoplastic resin ~or inner body to form an outer covering layer oriented in the direction of extrusion on said non-oriented inner resin body, and pelletizing the glass fiber roving enclosed within double structured layers into 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 wlth an emulsion of a thermoplastic resin which is compatible with the thermo-plastic resin to be used for extrusion coating. As mentioned above~ commercially available glass fiber roving generally employs a bundle of about 2,000 filamentsg each filament being in the order of about 10 micron3 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 ~hich is hydrophilic in nature previously with an aqueous resin emulsion which is low in viscosity9 each of the glass fiber ~ilaments 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 ~igo 5, glass fiber roving 4 is led into pre-treatment liquid bath 5 to 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 Ll while it is immersed in and passed through said liquid bath to thereby coating each element of glass fiber mono-filaments with the aqueous resin emulsion to be adhered thereon.
Immersion of the glass f'iber roving in said resin emulsion may simply be conducted by passing -through said resin emulsion which is contained in a conventional liquld bath. Alternatively, a vibrator such as ultra-sonic vibrator is provided in said emulsion liquid bath so as to vibrate the emulsion~ whereby the immersion effect(coating adhesion effect) can be complete and production speed can also be accelerated.
The amount o~ 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 resi,n content adhered after drying said emulsion9 preferably ]5 to 25
3 parts by weight9 per 100 parts by 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~
whileg an amount in excess of 30 parts by weight is difficult to be coated uniformly by once-thru immersion.
~or coating such a large amount of resin~ adhesion by way of several times repeated coating or any other specific device is required. For the purpose of the present invention9 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 conta:Lned in conventional commer-cially available emulsions~ thus requiring no specl~lc emulsion to be used.
The emulsion coated on the glass fiber roving
whileg an amount in excess of 30 parts by weight is difficult to be coated uniformly by once-thru immersion.
~or coating such a large amount of resin~ adhesion by way of several times repeated coating or any other specific device is required. For the purpose of the present invention9 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 conta:Lned in conventional commer-cially available emulsions~ thus requiring no specl~lc emulsion to be used.
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. Especiallya when drying ls conducted by use of a far infrared ray heater~ utilization efficiency of electricity is good. I'he lnternal atmosphere temperature in the heater 6 through whlch the glass fiber roving 4 is passed may sufficiently be about 100 to 350C. In case of some latices 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 150C.
The extruder may be any of conventionally used extruders for thermoplastic resins~ so long as it can feed stably a plastified molten resin without output irregularity to a die 8. The extrusion die ~ is provided for the purpose of extrusion coating of the glass fiber roving. It may be a die frequently used f'or wire coating9 etc. But, when five bundles of glass fiber roving are to be included within one pellet, for exampleg it is preferred to introduce five bundles of`
the emulsion treated glass fiber roving as described above individually one by one into said die. Further-more, it is also preferred to have a die structure which enables another coating9 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 g,lass fiber rovings~ which usually consist of a bundle of 500 to 20000 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 due to :Lnsufficient adhesion to the resT,n~ resulting in unfavorable scattering of such separated glass fibers.
The die structure~ which may differ depending on production speed~ is preferably such that the internal pressure in the resin may be increased and the pressure beared 'by the resin extruded may actuate in the direction of alleviating the drawing force imposed on said coated strandO ~?ig. 6 shows one example of the extrusion coating die for double coating.
The The heater 6 and the die 8 should prererably 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 withou-t too much cooling. For~ if a ~lass fiber roving having 5 % or- more of the emulsion adhered, which is considerably rigid, is abruptly flexed, there is a fear 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 coatin~ die ~ to a desired glass fiber- content is cooled in a cooling water bath 9 to be solidified and wound up by a roll 10. Said strand is pelletized by a pelletizer (cutting machine) 11 to a desired strength. Said 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 prefer-ably from 5 to 60 % by weight. With a content less than
The heater 6 may be any of those utilizing radiant heat such as nichrome wire heater~ etc or those utilizing heated air. Especiallya when drying ls conducted by use of a far infrared ray heater~ utilization efficiency of electricity is good. I'he lnternal atmosphere temperature in the heater 6 through whlch the glass fiber roving 4 is passed may sufficiently be about 100 to 350C. In case of some latices 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 150C.
The extruder may be any of conventionally used extruders for thermoplastic resins~ so long as it can feed stably a plastified molten resin without output irregularity to a die 8. The extrusion die ~ is provided for the purpose of extrusion coating of the glass fiber roving. It may be a die frequently used f'or wire coating9 etc. But, when five bundles of glass fiber roving are to be included within one pellet, for exampleg it is preferred to introduce five bundles of`
the emulsion treated glass fiber roving as described above individually one by one into said die. Further-more, it is also preferred to have a die structure which enables another coating9 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 g,lass fiber rovings~ which usually consist of a bundle of 500 to 20000 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 due to :Lnsufficient adhesion to the resT,n~ resulting in unfavorable scattering of such separated glass fibers.
The die structure~ which may differ depending on production speed~ is preferably such that the internal pressure in the resin may be increased and the pressure beared 'by the resin extruded may actuate in the direction of alleviating the drawing force imposed on said coated strandO ~?ig. 6 shows one example of the extrusion coating die for double coating.
The The heater 6 and the die 8 should prererably 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 withou-t too much cooling. For~ if a ~lass fiber roving having 5 % or- more of the emulsion adhered, which is considerably rigid, is abruptly flexed, there is a fear 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 coatin~ die ~ to a desired glass fiber- content is cooled in a cooling water bath 9 to be solidified and wound up by a roll 10. Said strand is pelletized by a pelletizer (cutting machine) 11 to a desired strength. Said 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 prefer-ably from 5 to 60 % by weight. With a content less than
5 % by weight~ there is no remarkable effect of reinforce-ment 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 emul-sion treatment is from 0.25 to 18 % by weight, while that by extrusion coating from 94.75 to 22 % by weight.
The thermoplastic resin to be used for the aqueous emulsion in the ~irst step and that for the extrusion c02t-ing may be of the same kind or 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 ~ below.
Table 2 Oriented resin (formed Non-oriented resin (formed Class by extrusion coating? from aqueous emulsion) 1 Polystyrene(including Polystyrene resin or rubber-modified high- Styrene-butadiene resin impact polystyrene) 2 Acrylonitrile-styrene Acrylonitrile-styrene resin 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) 3 Acrylonitrile-butadiene- 1'he same resin as in styrene resin; Methyl Class 29 or a resin of methacrylate-acrylo- the same kincl as the nitrile-styrene- oriented resin butadiene resin9 Methyl methacrylate-styrene-butadiene resinl or Acrylonitrile-butadiene-~-methyl styrene-styrene ~esin Ll Polyphenylene ether Polyphenylene etherg or modified poly- modified polyphenylene phenylene ether ether or polystyrene resin Polyethylene or Polyethyleneg poly-polypropylene propyleneg ethylene-vinyl 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 belowg which are measured by ISO R1133~1969 "Determination of the Melt ~low Rate of Thermoplastics" or a method similar thereto under conditions as given in the same Table.
Table 3 MFR measurement The range Thermoplastic conditions (tem- of MFR
resin v~lue Remarks Polystyrene 200C9 5 ~g 1 100 Rubber ~procedure ~) modified po ly~
styrene being included : Acrylonitrile- 220~g 10 kg 1 - 100 Acrylo-styrene nitrile/
styrene=
ABS type resin 220C, 10 kg 1 - 1~0 PPE 250C~ 10 kg 1 - 100 Modified PPE:
bein~;
included P~ 190C, 2.16 kg 0.03 - 100 (procedure 4) PP 230Cg 2.16 kg 0.1 - 100 (procedure 12) :
In the following Table 4 g there are shown the physical properties of the injection molded test pieces -~
prepared from the molding material of the present inven-tion utilizing AS resin as thermoplastic resin as obtained by the procedure as described in the following ~xample 1 as compared with those prepared by the methods of prior artg namely by blending chopped strands of glass fiber .-.
with molten AS resin (reference example l)g by applying only emulsion coating of AS resin on glass fiber roving (reference example 2)g 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 rovingg followed by extrusion coating of AS resin treference example 4)g using the same AS resins, respectively.
Table 4 Refer- Refer- Refer- Refer-ence ence ence ence AS example example example example Example resin 1 Z _ 3 4 ~
Pre-treatment None None AS None AS 20% AS
of glass emulsion MEK emulsion fiber treat- solu- treat-ment tion ment alone Glass fi~er content in solvent 20 20 20 20 20 separation method) Tensile strength 730 1100 1100 800 850 1200 JIS K6871) Elongation (%; JIS 2 2 2 2 2 2 K6871) Flexural strength 1070 1500 1400 1400 1300 1640 ASTM D790) Flexural (Kg/cm2; 35 7000062000 60000 55000 73000 ASTM D790) Izod impact 5-13 5-11 strength 1 5 5 0 7 (greatly (greatly 11 (Kg cm/cm~ ' fluc- fluc-JIS K6871) tuated) tuated) Heat distortion 70 99 99 95 98 102 temperature (Cj JIS K6871) Dispersion of bad(in-glass fibers suffi-(vis.ible good bad cient good observation glass of injection fiber molded plate) dis-persion) Table 4 (contld) Refer- Refer- Refer- Refer-ence ence ence ence AS example example example example Example resin 1 2 3 4 Average un- un-glass fiber measur_ measur-length in - 0.4 mm 0.75mm able due able due 1.2 mm the molded to the to the article presence presence (microscopic of glass of glass observation fiber fiber of glass balls balls fibers separated by solvent) Abrasion of inJection molding machine (visible None abraded abraded - - None observation af-ter half year operation) As apparently seen from ~able 4, the glass fiber reinforced thermoplastic resin molding composition of the present invention can produce injection molded articles having excellent physical properties9 being superior over commercially available glass fiber :
reinforced AS resin (reference example 1) in impact stren~th (Izod impact strength) by as much as twice, and also remarkably in heat~resistance (heat distortion temperature). Furthermoreg creep characteristics at a high temperature are also found to be extremel.y improvedO It is believed that such improvements in physical properties can be ascribed to uniform disper-sion of glass fiber filaments and longer average glass fiber length in the thermoplastic resin of the injection molded article produced from the pellet of the present invention. ~urthermore, 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 Lnjection molding machine can be f'ree from abrasion by use of the molding material of the present invention.
The present invention is further illustrated by the following Examples and ~omparison example.
Example 1 ~our bundles of glass fibers (2000 end, 13 ~
filaments in one bundle) are immersed in a AS resin (AN-25 %~ M.~.R.=5 g/10 min.) emulsion with 50 % solld compo-nents. The bundles subjected to coating treatment with said emulsion are dried under an atmosphere at 200C.
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 180C on the hopper side and 200 to 220C on the outflowing side and a die temperature o~ 220C at the rate o~ 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 s'crand is cut into pellets with 3.5 mm length by a pelletizer. The pellet obtained contains 20 wt.% of glass fibers~ l~ wt.% of non oriented AS resin and 76 wt.%
of oriented AS resin. The degree of orientation of the oriented AS resin is measured at 160C by the method as described above to be 1 % shrinkage. The pellet can be 8~L7 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 mo:Lding to obtain an article having physical properties as shown in Table L~.
In addition to the excellent physical properties as mentioned aboveg the dispersion of the glass fibers ln the molded article is found to be good without ag,glo-meration(balls) of glass ~ibers. 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 supplied from the extruder.
That isg melt flow properties of these resins are measured byg for example, Melt Flow Rate measuring device as determined in IS0 R1133 under the condition of 220C, 10 Kg load to give the same result of 5 g/10 min.
Example 2 ;
Example 1 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 anAS resin with a melt flow rate of 5 g/10 min. to be supplied from the extruderg under other-wise the same conditions as in Example 1, to prepare a pellet with strand diameter of 3.8 mm~ and length of 3.5 mm. By injection molding the resultant pellet by conventional methodg there is obtained a molded article which is bekter 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~ I~od impact strength is slightly improved to be 13 kg-cm/cm as compared with Example 19 other properties being comparable to those of Example 1.
Example 3 Four bundles of a glass fiber (2000 end~ 15 u~
mono~filaments in one bundle) are immersed in a styrene-butadiene resin (St~Bd=6/4) emulsion (solid componentsO
45 %) and dried at 110C. The emulsion coated bundles after drying contains 85 parts by weight of ~lass f'ibers and 15 parts by weight of styrene-butadiene resin.
A polystyrene resin is extruded throu~h an extruder maintained at a barrel temperature of 160 to 1~0C on the hopper side and 200 to 220C on the outlet side and a die temperature of 220C and supplied to an extrusion coating dieO The glass fiber is wound up at a speed of 5 ~.~min. with extruded strand diameter being 3.2 mm~. Said strand is cut into pellets of 5 mm length. Said pellets contain 30 wt.% of the glass f'ibers~ 5.3 wt.% of non-oriented SB resin and 64.7 wt.~ 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 an injection molded article having improved physical properties. The styrene-butadiene 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 IS0-R1133~ procedure 8).
Example 4 Three bundles of glass fiber (each bundle comprising 2000 end filaments with diameters of 13 ~) are immersed in an aqueous polystyrene resin emulsion with solid content of 40 % to apply coating treatmen~ on each roving~ followed by drying in an atmosphere main-tained at 200C. The composition of the roving coated with polystyrene resin after drying consists of ~5 parts by weight of glass fiber and 15 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 270Cg respectively at the rate of 75 kg/hour to be fed into the dieO On the other hand, winding speed of the glass fiber roving as prepared above ls controlled at 20 rn/minute with diameter of extrusion coated strand of 3.2 mm, five strands being wound up at one time. The resultant strand is cut into pellets by a pelletizerO 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 145C. ~or comparative purpose, there are prepared pellets of a mixture of the polyphenylene ether mixture with 20 % of glass flber 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 140C. From this comparison, the improved effect of the present invention can be apparently 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 ~ibersg exhibiting a good appearance.
Example 5 Example 1 is repeated except that an a~ueous emulsion (solid: 50 %) of ethylene-vinyl acetate copolymer (vinyl acetate 28 %) is used in place of the AS emulsiong and a high density polyethylene (density=0.950, MX=
3 g/10 min) in place of the AS resin for the extrusion coated outer coverihg layer resin. The resultant molding material produces a molded article improved in mechanical properties to the same extent as observed in Éxa~p~e 1.
Comparison example lg ~n substantially the same step as in Example 1 in place of the AS resin emulsion~ there is prepared a 20 wto% 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 rovlng as used in Example 1 is immersed in said AS resin solutiong followed by drying. The roving after drying contalns 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 weightg followed by pelletizingO The pellets obtained are injection molded to ob~ain an injection molded articleg in which glass fibers are insufficiently dispersed. The injection molded articles have various fluctuations in physical pro~erties~ especially Izod impact stren~th.
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 solutiong penetration degree of the resin solution into the roving and balance in amounts of the coating or adhesion of the resin on the roving, it ls 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 coatinK can be applied previously on the glass fibers.
As described above, the moldlng material of the glass ~iber reinforced thermoplastlc 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 in~ection molding machine or an ext~uder 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 present invention~ it can produce molded articles with excellent physical properties and surface appearance of good smoothness and gloss. Furthermoreg 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 abrasion of machines is very small. Thusg a variety of uses will be expected of the materi~l provided by the present invention.
~ 2~ _
The thermoplastic resin to be used for the aqueous emulsion in the ~irst step and that for the extrusion c02t-ing may be of the same kind or 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 ~ below.
Table 2 Oriented resin (formed Non-oriented resin (formed Class by extrusion coating? from aqueous emulsion) 1 Polystyrene(including Polystyrene resin or rubber-modified high- Styrene-butadiene resin impact polystyrene) 2 Acrylonitrile-styrene Acrylonitrile-styrene resin 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) 3 Acrylonitrile-butadiene- 1'he same resin as in styrene resin; Methyl Class 29 or a resin of methacrylate-acrylo- the same kincl as the nitrile-styrene- oriented resin butadiene resin9 Methyl methacrylate-styrene-butadiene resinl or Acrylonitrile-butadiene-~-methyl styrene-styrene ~esin Ll Polyphenylene ether Polyphenylene etherg or modified poly- modified polyphenylene phenylene ether ether or polystyrene resin Polyethylene or Polyethyleneg poly-polypropylene propyleneg ethylene-vinyl 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 belowg which are measured by ISO R1133~1969 "Determination of the Melt ~low Rate of Thermoplastics" or a method similar thereto under conditions as given in the same Table.
Table 3 MFR measurement The range Thermoplastic conditions (tem- of MFR
resin v~lue Remarks Polystyrene 200C9 5 ~g 1 100 Rubber ~procedure ~) modified po ly~
styrene being included : Acrylonitrile- 220~g 10 kg 1 - 100 Acrylo-styrene nitrile/
styrene=
ABS type resin 220C, 10 kg 1 - 1~0 PPE 250C~ 10 kg 1 - 100 Modified PPE:
bein~;
included P~ 190C, 2.16 kg 0.03 - 100 (procedure 4) PP 230Cg 2.16 kg 0.1 - 100 (procedure 12) :
In the following Table 4 g there are shown the physical properties of the injection molded test pieces -~
prepared from the molding material of the present inven-tion utilizing AS resin as thermoplastic resin as obtained by the procedure as described in the following ~xample 1 as compared with those prepared by the methods of prior artg namely by blending chopped strands of glass fiber .-.
with molten AS resin (reference example l)g by applying only emulsion coating of AS resin on glass fiber roving (reference example 2)g 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 rovingg followed by extrusion coating of AS resin treference example 4)g using the same AS resins, respectively.
Table 4 Refer- Refer- Refer- Refer-ence ence ence ence AS example example example example Example resin 1 Z _ 3 4 ~
Pre-treatment None None AS None AS 20% AS
of glass emulsion MEK emulsion fiber treat- solu- treat-ment tion ment alone Glass fi~er content in solvent 20 20 20 20 20 separation method) Tensile strength 730 1100 1100 800 850 1200 JIS K6871) Elongation (%; JIS 2 2 2 2 2 2 K6871) Flexural strength 1070 1500 1400 1400 1300 1640 ASTM D790) Flexural (Kg/cm2; 35 7000062000 60000 55000 73000 ASTM D790) Izod impact 5-13 5-11 strength 1 5 5 0 7 (greatly (greatly 11 (Kg cm/cm~ ' fluc- fluc-JIS K6871) tuated) tuated) Heat distortion 70 99 99 95 98 102 temperature (Cj JIS K6871) Dispersion of bad(in-glass fibers suffi-(vis.ible good bad cient good observation glass of injection fiber molded plate) dis-persion) Table 4 (contld) Refer- Refer- Refer- Refer-ence ence ence ence AS example example example example Example resin 1 2 3 4 Average un- un-glass fiber measur_ measur-length in - 0.4 mm 0.75mm able due able due 1.2 mm the molded to the to the article presence presence (microscopic of glass of glass observation fiber fiber of glass balls balls fibers separated by solvent) Abrasion of inJection molding machine (visible None abraded abraded - - None observation af-ter half year operation) As apparently seen from ~able 4, the glass fiber reinforced thermoplastic resin molding composition of the present invention can produce injection molded articles having excellent physical properties9 being superior over commercially available glass fiber :
reinforced AS resin (reference example 1) in impact stren~th (Izod impact strength) by as much as twice, and also remarkably in heat~resistance (heat distortion temperature). Furthermoreg creep characteristics at a high temperature are also found to be extremel.y improvedO It is believed that such improvements in physical properties can be ascribed to uniform disper-sion of glass fiber filaments and longer average glass fiber length in the thermoplastic resin of the injection molded article produced from the pellet of the present invention. ~urthermore, 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 Lnjection molding machine can be f'ree from abrasion by use of the molding material of the present invention.
The present invention is further illustrated by the following Examples and ~omparison example.
Example 1 ~our bundles of glass fibers (2000 end, 13 ~
filaments in one bundle) are immersed in a AS resin (AN-25 %~ M.~.R.=5 g/10 min.) emulsion with 50 % solld compo-nents. The bundles subjected to coating treatment with said emulsion are dried under an atmosphere at 200C.
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 180C on the hopper side and 200 to 220C on the outflowing side and a die temperature o~ 220C at the rate o~ 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 s'crand is cut into pellets with 3.5 mm length by a pelletizer. The pellet obtained contains 20 wt.% of glass fibers~ l~ wt.% of non oriented AS resin and 76 wt.%
of oriented AS resin. The degree of orientation of the oriented AS resin is measured at 160C by the method as described above to be 1 % shrinkage. The pellet can be 8~L7 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 mo:Lding to obtain an article having physical properties as shown in Table L~.
In addition to the excellent physical properties as mentioned aboveg the dispersion of the glass fibers ln the molded article is found to be good without ag,glo-meration(balls) of glass ~ibers. 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 supplied from the extruder.
That isg melt flow properties of these resins are measured byg for example, Melt Flow Rate measuring device as determined in IS0 R1133 under the condition of 220C, 10 Kg load to give the same result of 5 g/10 min.
Example 2 ;
Example 1 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 anAS resin with a melt flow rate of 5 g/10 min. to be supplied from the extruderg under other-wise the same conditions as in Example 1, to prepare a pellet with strand diameter of 3.8 mm~ and length of 3.5 mm. By injection molding the resultant pellet by conventional methodg there is obtained a molded article which is bekter 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~ I~od impact strength is slightly improved to be 13 kg-cm/cm as compared with Example 19 other properties being comparable to those of Example 1.
Example 3 Four bundles of a glass fiber (2000 end~ 15 u~
mono~filaments in one bundle) are immersed in a styrene-butadiene resin (St~Bd=6/4) emulsion (solid componentsO
45 %) and dried at 110C. The emulsion coated bundles after drying contains 85 parts by weight of ~lass f'ibers and 15 parts by weight of styrene-butadiene resin.
A polystyrene resin is extruded throu~h an extruder maintained at a barrel temperature of 160 to 1~0C on the hopper side and 200 to 220C on the outlet side and a die temperature of 220C and supplied to an extrusion coating dieO The glass fiber is wound up at a speed of 5 ~.~min. with extruded strand diameter being 3.2 mm~. Said strand is cut into pellets of 5 mm length. Said pellets contain 30 wt.% of the glass f'ibers~ 5.3 wt.% of non-oriented SB resin and 64.7 wt.~ 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 an injection molded article having improved physical properties. The styrene-butadiene 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 IS0-R1133~ procedure 8).
Example 4 Three bundles of glass fiber (each bundle comprising 2000 end filaments with diameters of 13 ~) are immersed in an aqueous polystyrene resin emulsion with solid content of 40 % to apply coating treatmen~ on each roving~ followed by drying in an atmosphere main-tained at 200C. The composition of the roving coated with polystyrene resin after drying consists of ~5 parts by weight of glass fiber and 15 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 270Cg respectively at the rate of 75 kg/hour to be fed into the dieO On the other hand, winding speed of the glass fiber roving as prepared above ls controlled at 20 rn/minute with diameter of extrusion coated strand of 3.2 mm, five strands being wound up at one time. The resultant strand is cut into pellets by a pelletizerO 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 145C. ~or comparative purpose, there are prepared pellets of a mixture of the polyphenylene ether mixture with 20 % of glass flber 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 140C. From this comparison, the improved effect of the present invention can be apparently 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 ~ibersg exhibiting a good appearance.
Example 5 Example 1 is repeated except that an a~ueous emulsion (solid: 50 %) of ethylene-vinyl acetate copolymer (vinyl acetate 28 %) is used in place of the AS emulsiong and a high density polyethylene (density=0.950, MX=
3 g/10 min) in place of the AS resin for the extrusion coated outer coverihg layer resin. The resultant molding material produces a molded article improved in mechanical properties to the same extent as observed in Éxa~p~e 1.
Comparison example lg ~n substantially the same step as in Example 1 in place of the AS resin emulsion~ there is prepared a 20 wto% 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 rovlng as used in Example 1 is immersed in said AS resin solutiong followed by drying. The roving after drying contalns 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 weightg followed by pelletizingO The pellets obtained are injection molded to ob~ain an injection molded articleg in which glass fibers are insufficiently dispersed. The injection molded articles have various fluctuations in physical pro~erties~ especially Izod impact stren~th.
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 solutiong penetration degree of the resin solution into the roving and balance in amounts of the coating or adhesion of the resin on the roving, it ls 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 coatinK can be applied previously on the glass fibers.
As described above, the moldlng material of the glass ~iber reinforced thermoplastlc 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 in~ection molding machine or an ext~uder 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 present invention~ it can produce molded articles with excellent physical properties and surface appearance of good smoothness and gloss. Furthermoreg 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 abrasion of machines is very small. Thusg a variety of uses will be expected of the materi~l provided by the present invention.
~ 2~ _
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A molding material structure which comprises (1) at least one inner piller-shaped body, each comprising a bundle of glass fiber filaments and a non-oriented thermoplastic 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 pillar-shaped body wherein glass fiber content in the composition is from 5 to 60 % by weight, the proportion of the thermoplastic resin in the inner body from 0.25 to 18 % by weight and that in the outer layer from 94.75 to 22 % by weight, each being based on the total composition and the length of the structure is from 1-20 mm.
2. A molding material structure of a thermoplastic resin composition as in claim 1, wherein the thermoplastic resin for the outer layer is selected from the group consisting of polystyrene and rubber-modified high-impact polystyrene and that for the inner body from the group consisting of polystyrene and stylene-butadiene copolymer.
3. A molding material structure as in claim 1, wherein the thermoplastic resin for the outer layer is selected from the group consisting of acrylonitrile-styrene copolymer and that for the inner body from the group consisting of acrylonitrile-styrene copolymer and copolymers of styrene with at least one monomer selected from the group consisting of acrylonitrile, acrylic acid and its derivative, and methacrylic acid and its derivative.
4. A molding material structure as in claim 1, wherein the thermoplastic resin for the outer layer is selected from the group consisting of acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-acrylonitrile-styrene-butadiene copolymer, methyl methacrylate-styrene-butadiene copolymer and acrylo-nitrile-butadiene-.alpha.-methyl styrene-styrene copolymer and that for the inner body from the group consisting of acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-acrylonitrile-styrene-butadiene copolymer, methyl methacrylate-sytrene-butadiene copolymer, acrylonitrile-butadiene-.alpha.-methyl styrene-styrene copolymer, acrylonitrile-styrene copolymer, and copolymers of styrene with at least one monomer selected from the group consisting of acrylonitrile, acrylic acid and its derivative, and methacrylic acid and its derivative.
5. A molding material structure as in claim 1, wherein the thermoplastic resin for the outer layer is polyphenylene ether and modified polyphenylene ether and that for the inner body from the group consisting of polyphenylene ether, modified polyphenylene ether and polystyrene.
6. A molding material structure as in claim 1, wherein the thermoplastic resin for the outer layer is selected from the group consisting of polyethylene and polypropylene and that for the inner body from the group consisting of polyethylene, polypropylene, ethylene-vinyl acetate copolymer and ethylenic ionomer.
7. A molding material structure as in claim 1, wherein the thermoplastic resin for the outer layer and that for the inner body are of the same kind of a thermoplastic resin.
8. A molding material structure as in claim 1, wherein the thermoplastic resin for the outer layer has a melt flow rate not higher than that for the inner body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA301,396A CA1108817A (en) | 1978-04-18 | 1978-04-18 | Molding material structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA301,396A CA1108817A (en) | 1978-04-18 | 1978-04-18 | Molding material structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1108817A true CA1108817A (en) | 1981-09-15 |
Family
ID=4111278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA301,396A Expired CA1108817A (en) | 1978-04-18 | 1978-04-18 | Molding material structure |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1108817A (en) |
-
1978
- 1978-04-18 CA CA301,396A patent/CA1108817A/en not_active Expired
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