CA2130120A1 - Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same - Google Patents
Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the sameInfo
- Publication number
- CA2130120A1 CA2130120A1 CA 2130120 CA2130120A CA2130120A1 CA 2130120 A1 CA2130120 A1 CA 2130120A1 CA 2130120 CA2130120 CA 2130120 CA 2130120 A CA2130120 A CA 2130120A CA 2130120 A1 CA2130120 A1 CA 2130120A1
- Authority
- CA
- Canada
- Prior art keywords
- mold
- thermoplastic resin
- coating
- resin
- high modulus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
- 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
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/902—High modulus filament or fiber
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2904—Staple length fiber
- Y10T428/2905—Plural and with bonded intersections only
-
- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/659—Including an additional nonwoven fabric
-
- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/697—Containing at least two chemically different strand or fiber materials
Abstract
A process is provided for preparing recyclable reinforced composite structures having enhanced surface appearance by heating a self-supporting porous batt comprised of an intimate homogenous blend of high modulus reinforcing fibers and thermoplastic resin fibers to a temperature sufficient to melt the resin component and convert the batt into moldable form, placing the moldable batt into a heated mold to flow, solidify and substantially crystallize the resin component, introducing a thermosetting resin-containing coating material into the mold adjacent at least one surface of the crystallized structure to provide a coating on the one surface and dwelling the coated structure in the mold for a time sufficient to set the coating material.
Description
WO g3/16~56 PCr/~J~;92/~1391 TI~
RECYC~BLE MOLDED HIGH MODIJLUS
FIBER REINFORC~D THERMOPLASTIC Sl~IJCI~URES
AND PROCESS FOR PREPARING THE SAME
FIE~LD~:)F ~E TNV~ON
The presen~ invention relates to pr~viding re~clable high modulus ffber reinorced composite stmctures h~ing an enhanced surface appearance.
~
lhe use of plastic componen~s irl combination with met~l parts is comm~n in ~he production of ~utomobiles. M~ures of resins and rei~orcing materials are used as sheet molding cornpounds, SMCs~ which are ~olded to form vario~s shaped ar~icles. Generally in applications requiring 5 high quality painted surfaces9 highly ~lled ~hermose~ting SMCs haYe bee used.
~ lo~g standing problem ill providing rei~forced composi~e structures resides ill m~nufacturi~g s~uctures which w~en pain~ed provide a Class A~ ~ish.
These structures such as automotiYe body panels must be capable of being 20 prooessed ill assem~ly plants with steel paIlels. Th~y must be able to survive assembly plant condi~ior~, painting and baldng? where ma~imum metal ~ :~
temperatures can reach 200C ~or as long as 30 minutes with surface coatings - remaini~g ~:~mly adherred to the sllbstrate and retaining tbeir Cl~ss A
appearance. The body panels must haYe, after prucessing" an ~ppearance 5 that is comparable to d~e appearaa~e of an adjoining part m~de of steel.
They must also have accep~able dimensional s~ability in order ~o maintain the highest ~quali~ ht and finish oYer u~de temperature ex~remes folmd in YarioU5 geograp}~ market segments. When us~l~g SMCs, surace appearance problems such as "paint pops" ocsur due to em~ssion of low :~.
30 molécul~r weight monomers in the thermose~ting subs~ate, In addition an eYer ~ncreas~ng concern is whether the mater~al is readily recyclable during m~facture ~Ild in post manufacture use. For example, call the resin compone~t be remelted or depolymerized. llle thermosetting SMCs are not ~-re~yclab}e in the sense that they cannot be remelted or depolymenzed.
wo 93/16856 Pcr/uss2/0l3g1 2 130 ~Z0 - 2 S.lIMMARY OF~E INVENllON
The products of this invention which solve the problems noted above are made by preparing composite s~ructures comprised of a substrate prepared from a plurali~r of layers of a self-supporting porous web comprised 5 of randomly dispersed high modulus reinforcing fibers held together by solidified the~moplastic resir~. The layers are heate~pr~v~a~Fe~nold fvrm whi~h is then placed in a mold to flow,-solidi~y, and crystallize ~he thermopl~stic resin. The resulting rei~orced thermoplastic substrate is coated in the mold with a thin coa~ing of a thermoset~ing resin-cont~ng 10 compositio~. f'~
In preparing~the composite structures of the invention, the layers of porous web ar~ stacked together to form a batt which is h~ated in a convection oven to so~vert the batt into a moldable form. The number of l.ayers is determined by weighing the precut shapes to provide a predetermined mold charge mass whi~ is based Oll the final dQsired m~lded - p~ thic~ess. Ihe moldable form is ~en placed in a heated mold. ~he mold is closed and pressure is applied to flow mold the preform ~o folm a consolidated pa~t and to crystallize the thermoplas~ic resin component.
Upon cGmpletio~ of the molding operation, the mold halves are separated 2 0 and/or the pressllre is released to pennit introductioIl of a thermosetti~g resin-contai~ing coating material. The rnold is then closed, arld under pressure~ ~he material spreads over the s~ ace of the molded preform.
Heating under pressure is continued for a time suffïcie~lt to se~ the coating compositio~. Surprisi~gly, the thermosetting composition adheres 2 5 tenaciously to ~Ihe reir~orced molde~ thermoplas~ic su~strate a~d exhibits outstanding surPace appearaIlce.
T~e batts used to prepare the pre~orms are comprised of f~om S to 50 perce~t by weight glass fibers a~d from 50 to 95 percent by weight thermopl~stic resin T~e batts are air permeable a~d are made ~rom air 3 o - permeable webs of raTldomly dispe~sed high modulus ~bers held together at fiber crossover locatio~s by solidifîed globules of thermoplastic resin erl~elopi~g the fibers at the crossoYer locations. Some of the randomly dispersed fibers have bead-like drops of solidified the~moplastic resin adhered thereto at locations along their leng~h at locations othe~ than at 3 5 crossovers. The preparation of such webs is disclosed in Geary and Weeks WO 93/16856 PCl`/US92/0~3~1 3 2130~
US Paten~ Application No. 07/606,651~ filed October 31, 199û and European Patent Applica~ion 0 341 977, published November 15, 1g89.
The products of this in~rention are composite structures which are warp-free, haYe very smooth surfaces and exhibit exeellent physical proper~ies The ~hermosetting resin-containing surface coating strollgly adheres to the reinforced molded thermoplastic substrate surf~ce. When the stmctures are used irl automotive body panels and painted, the painted su~ace is rated Class "~". The quality of the surface coatiTIg can be measured usin~ a commercially available dis~inctness of image (DOI) meter.
Reflected light i~tensity ~rom a photo detector is measur~d as a function of the scatterill~g allgle. If the scatterillg fun~ion is sho~ and wide, the surface is said to have a low DOI. If the scatte~g is limited, the surface has a high DC)I. DOI meters detect the re~ected light in a region slightly away ~rorn the spectral axlgle. If the ligh$ detected is small, the distinctrless is high. DOI is measured on.a scale ~rom ~ to 100 wi~h 10û bei~g the highest l~vel of smoothIless.
Paintin~g procedures which are well kn~wn in the art may be used with the structures of ~his invention. They may be painted side by side with steel parts. For example~ the surfaces may be primed and topcoated, or 2 0 optionally a basecoat/clear coat fiuish may be applled. When placed in a drying ~veIl after being painted, no "pai~t pops" occur whereas in using SMCs, due to em~ssion of low molecula~ weight monomers~ "paint pops" are e~cvuntered.
BRIEF DESCRIP~C)N QF~E DRA~(~S
FIG. 1 is a schematic illustration of a ~oss section of a composi~e structure produced by the process of this inYeIltioIl.
DETAIL~D DE~IQN OF THE INVENrrION
Referring to the drawing, ~ig. 1 shows reinforced therIIloplastic subs~ 10 w~ich has been coated with thermosetting resin-~oDtaining 3 o co~ing 12. l he res~ ing composi~e part is coated with mul~iple layers of paint 14.
In c~ng out ~he process of the ir~vention, a porous batt is formed ~om an intimate homogenousblend of rein~orcing ~lber ~d theImoplastic resin fiber components. The reir~orcing fiber may be any high 3 5 modulus f;ber, such as polyamides, glass, carbon~ polyesters and high temperahlre nylons. A modulus of at least 100,000 M Pascals is preferred.
Pcr/US92/013 ~VO 93116~5b . 1 :
? ~30 1~
fibers may be of consistent length o ~Iy long fibers in the range of one ~re preferred. I
plastic resin fibers may b~ any th p f era~isuitablethermoplasticsfor pp p~ cs incIude~ but are n~t l~ t b sters COpolyesters7 polyamides~ inc EEg 1 N lon 1~ d ~2, polyetheretherketo pOlyetherlce~oneketon~ (PEK~) o~ thYlPhenYlen~' plYaIYlateiS
~d ride Theaeniersindlengthofth t th~ ~olume of a single fiber is unt 4 10 1~ 3 mm3 Which when heated re ge of approximately 0-5 ~ 10 to h riioplasticfiberdiameterisgene Y
id tioDS For instance~ the most econ Slalnent (DPF). In general, a leng of ~reater tban 05 is preferrgd-t Iy blended web if formed from tbe i~
fib rs ThebasiSweightoftheforlned ds per square foot (O 244 - 0.98 kgl q d tbrough a corivection heatmg oven y d fib rfor~DingglObuleswhichbondth d a web of 5ubstantial strength S~i idca'~ to Obtairdng a web that hslS th g b querlt ~nvec~ivn hea~g in pr~p t~g res~ co~ai~ing coating co~p ;I~S W~ich are re~dered illsoluble }~ esiIls are ~rell know~ in the art a~
nson and ~ampbell in ~hapter 7~ ~
3 o published by IN~R CE puBLISHERS. ~C., New york~ 19 I d polyesterlac~yliclqinylmonome f pOlyester~ aCIylic and qinyl mon Ik d and un5aturated polyester resin cLOpEDlA, 1989 Edition~published b~
New ~ork, may be used-WO 93/16B56 P~/US92~01391 213012~
The thermosetting coating compositions can be i~lled or compouIlded to give the desired viscosi~ and flow charac~eris~iss ~or molding and to a~ord the desired physical proper~ies in the resulting coa~ng.
Examples of such ffllers or compolmding ingredients are iïllers like clay, talc,magnesium oxide, ma~esium hydroxide~ calcium carbonate aIld C~
silicate, mold release agents, colorants such as red iron oxide, titanium oxide,carbon blacl~ organic color pigments such as phthalo~yanine blue or green, an~idegradal~ts, W absorbers, calcium silicate, holl~w glass or resin micro-spheres, tbicl~ening agents, inhibitors and the like. Care should be exercised lo in ~e use of high filler coIltents as this may give high viscosities and result in ~w and h~dling di~culties.
A preferred thermosetting resin-containing composition consists of a styrene con~aining modi~ed acrylic resin mixture which is sold by GenCorp I~c. under the ~rademark Genglaze~. :
1~ A pre~er~e.d reinforcing i;ber used in the i~ve~ion is glass ~ber which consis~s of conventional spun glass strand having a diame~er between S - - -~
and 50 microns and a cllt length of 1 ~o 8 cm. As is common in the industry, ~:
such glass LS sized and chopped to length and shipped "wetn in moisture proof containers to the ~ustomer. A preferred mateIial is tha~ svld by ~ens- ~
Corn~g ~iberglass (OCF) under the label 133~ :-The pre~erred molding method for practi~ng the invention is compression molding. ~ stack of sheets are layered t~ether. The stack is ~:
plaG~d in a forced air comrection oven and heated ab~ve the melti~g point of the the~noplastic resin component for less than one minute. The heated ~ `
2 5 preform is then placed in a compression mold where the tool temperature is adjusted to a temperatllre to c~ystallize the the~oplastic resin component.
S~cient pressllre is applied ~o fl~w mold the preform ~o fill ~t the mold.
~er a dwell time of preferably 30 to 6û seconds the mold is opened. As soon a~s p~ssible after opeI~ing the mold, a thermoset~ing resin-corltaining ~:
3 o compo~ellt is introduced into the mold in a~ amount sllfficieIlt $o create a l~yer rom 3 to 10 mils (0.076 to 0.254 mm) ~hick over the upper ~urface of the prefo~m. Ihe coated structure is held in the mold under pressure for a ~zime suf~cient ~o cure the the~nosetting resin-containing component. The coated structure is pen~tted to ~ol sufficiently for handling and is then removed from the mold.
PCr/lJS~2/0 Wo 93/16~56 213~2~ 6 ion mo~ding the mold must be ope f coating composition in the mold on coated. ln allother ~e of mOlding, such as iniecti~n molding~ the mold lS
insert t~e charge means~ i-e- ope}ling . Y
RECYC~BLE MOLDED HIGH MODIJLUS
FIBER REINFORC~D THERMOPLASTIC Sl~IJCI~URES
AND PROCESS FOR PREPARING THE SAME
FIE~LD~:)F ~E TNV~ON
The presen~ invention relates to pr~viding re~clable high modulus ffber reinorced composite stmctures h~ing an enhanced surface appearance.
~
lhe use of plastic componen~s irl combination with met~l parts is comm~n in ~he production of ~utomobiles. M~ures of resins and rei~orcing materials are used as sheet molding cornpounds, SMCs~ which are ~olded to form vario~s shaped ar~icles. Generally in applications requiring 5 high quality painted surfaces9 highly ~lled ~hermose~ting SMCs haYe bee used.
~ lo~g standing problem ill providing rei~forced composi~e structures resides ill m~nufacturi~g s~uctures which w~en pain~ed provide a Class A~ ~ish.
These structures such as automotiYe body panels must be capable of being 20 prooessed ill assem~ly plants with steel paIlels. Th~y must be able to survive assembly plant condi~ior~, painting and baldng? where ma~imum metal ~ :~
temperatures can reach 200C ~or as long as 30 minutes with surface coatings - remaini~g ~:~mly adherred to the sllbstrate and retaining tbeir Cl~ss A
appearance. The body panels must haYe, after prucessing" an ~ppearance 5 that is comparable to d~e appearaa~e of an adjoining part m~de of steel.
They must also have accep~able dimensional s~ability in order ~o maintain the highest ~quali~ ht and finish oYer u~de temperature ex~remes folmd in YarioU5 geograp}~ market segments. When us~l~g SMCs, surace appearance problems such as "paint pops" ocsur due to em~ssion of low :~.
30 molécul~r weight monomers in the thermose~ting subs~ate, In addition an eYer ~ncreas~ng concern is whether the mater~al is readily recyclable during m~facture ~Ild in post manufacture use. For example, call the resin compone~t be remelted or depolymerized. llle thermosetting SMCs are not ~-re~yclab}e in the sense that they cannot be remelted or depolymenzed.
wo 93/16856 Pcr/uss2/0l3g1 2 130 ~Z0 - 2 S.lIMMARY OF~E INVENllON
The products of this invention which solve the problems noted above are made by preparing composite s~ructures comprised of a substrate prepared from a plurali~r of layers of a self-supporting porous web comprised 5 of randomly dispersed high modulus reinforcing fibers held together by solidified the~moplastic resir~. The layers are heate~pr~v~a~Fe~nold fvrm whi~h is then placed in a mold to flow,-solidi~y, and crystallize ~he thermopl~stic resin. The resulting rei~orced thermoplastic substrate is coated in the mold with a thin coa~ing of a thermoset~ing resin-cont~ng 10 compositio~. f'~
In preparing~the composite structures of the invention, the layers of porous web ar~ stacked together to form a batt which is h~ated in a convection oven to so~vert the batt into a moldable form. The number of l.ayers is determined by weighing the precut shapes to provide a predetermined mold charge mass whi~ is based Oll the final dQsired m~lded - p~ thic~ess. Ihe moldable form is ~en placed in a heated mold. ~he mold is closed and pressure is applied to flow mold the preform ~o folm a consolidated pa~t and to crystallize the thermoplas~ic resin component.
Upon cGmpletio~ of the molding operation, the mold halves are separated 2 0 and/or the pressllre is released to pennit introductioIl of a thermosetti~g resin-contai~ing coating material. The rnold is then closed, arld under pressure~ ~he material spreads over the s~ ace of the molded preform.
Heating under pressure is continued for a time suffïcie~lt to se~ the coating compositio~. Surprisi~gly, the thermosetting composition adheres 2 5 tenaciously to ~Ihe reir~orced molde~ thermoplas~ic su~strate a~d exhibits outstanding surPace appearaIlce.
T~e batts used to prepare the pre~orms are comprised of f~om S to 50 perce~t by weight glass fibers a~d from 50 to 95 percent by weight thermopl~stic resin T~e batts are air permeable a~d are made ~rom air 3 o - permeable webs of raTldomly dispe~sed high modulus ~bers held together at fiber crossover locatio~s by solidifîed globules of thermoplastic resin erl~elopi~g the fibers at the crossoYer locations. Some of the randomly dispersed fibers have bead-like drops of solidified the~moplastic resin adhered thereto at locations along their leng~h at locations othe~ than at 3 5 crossovers. The preparation of such webs is disclosed in Geary and Weeks WO 93/16856 PCl`/US92/0~3~1 3 2130~
US Paten~ Application No. 07/606,651~ filed October 31, 199û and European Patent Applica~ion 0 341 977, published November 15, 1g89.
The products of this in~rention are composite structures which are warp-free, haYe very smooth surfaces and exhibit exeellent physical proper~ies The ~hermosetting resin-containing surface coating strollgly adheres to the reinforced molded thermoplastic substrate surf~ce. When the stmctures are used irl automotive body panels and painted, the painted su~ace is rated Class "~". The quality of the surface coatiTIg can be measured usin~ a commercially available dis~inctness of image (DOI) meter.
Reflected light i~tensity ~rom a photo detector is measur~d as a function of the scatterill~g allgle. If the scatterillg fun~ion is sho~ and wide, the surface is said to have a low DOI. If the scatte~g is limited, the surface has a high DC)I. DOI meters detect the re~ected light in a region slightly away ~rorn the spectral axlgle. If the ligh$ detected is small, the distinctrless is high. DOI is measured on.a scale ~rom ~ to 100 wi~h 10û bei~g the highest l~vel of smoothIless.
Paintin~g procedures which are well kn~wn in the art may be used with the structures of ~his invention. They may be painted side by side with steel parts. For example~ the surfaces may be primed and topcoated, or 2 0 optionally a basecoat/clear coat fiuish may be applled. When placed in a drying ~veIl after being painted, no "pai~t pops" occur whereas in using SMCs, due to em~ssion of low molecula~ weight monomers~ "paint pops" are e~cvuntered.
BRIEF DESCRIP~C)N QF~E DRA~(~S
FIG. 1 is a schematic illustration of a ~oss section of a composi~e structure produced by the process of this inYeIltioIl.
DETAIL~D DE~IQN OF THE INVENrrION
Referring to the drawing, ~ig. 1 shows reinforced therIIloplastic subs~ 10 w~ich has been coated with thermosetting resin-~oDtaining 3 o co~ing 12. l he res~ ing composi~e part is coated with mul~iple layers of paint 14.
In c~ng out ~he process of the ir~vention, a porous batt is formed ~om an intimate homogenousblend of rein~orcing ~lber ~d theImoplastic resin fiber components. The reir~orcing fiber may be any high 3 5 modulus f;ber, such as polyamides, glass, carbon~ polyesters and high temperahlre nylons. A modulus of at least 100,000 M Pascals is preferred.
Pcr/US92/013 ~VO 93116~5b . 1 :
? ~30 1~
fibers may be of consistent length o ~Iy long fibers in the range of one ~re preferred. I
plastic resin fibers may b~ any th p f era~isuitablethermoplasticsfor pp p~ cs incIude~ but are n~t l~ t b sters COpolyesters7 polyamides~ inc EEg 1 N lon 1~ d ~2, polyetheretherketo pOlyetherlce~oneketon~ (PEK~) o~ thYlPhenYlen~' plYaIYlateiS
~d ride Theaeniersindlengthofth t th~ ~olume of a single fiber is unt 4 10 1~ 3 mm3 Which when heated re ge of approximately 0-5 ~ 10 to h riioplasticfiberdiameterisgene Y
id tioDS For instance~ the most econ Slalnent (DPF). In general, a leng of ~reater tban 05 is preferrgd-t Iy blended web if formed from tbe i~
fib rs ThebasiSweightoftheforlned ds per square foot (O 244 - 0.98 kgl q d tbrough a corivection heatmg oven y d fib rfor~DingglObuleswhichbondth d a web of 5ubstantial strength S~i idca'~ to Obtairdng a web that hslS th g b querlt ~nvec~ivn hea~g in pr~p t~g res~ co~ai~ing coating co~p ;I~S W~ich are re~dered illsoluble }~ esiIls are ~rell know~ in the art a~
nson and ~ampbell in ~hapter 7~ ~
3 o published by IN~R CE puBLISHERS. ~C., New york~ 19 I d polyesterlac~yliclqinylmonome f pOlyester~ aCIylic and qinyl mon Ik d and un5aturated polyester resin cLOpEDlA, 1989 Edition~published b~
New ~ork, may be used-WO 93/16B56 P~/US92~01391 213012~
The thermosetting coating compositions can be i~lled or compouIlded to give the desired viscosi~ and flow charac~eris~iss ~or molding and to a~ord the desired physical proper~ies in the resulting coa~ng.
Examples of such ffllers or compolmding ingredients are iïllers like clay, talc,magnesium oxide, ma~esium hydroxide~ calcium carbonate aIld C~
silicate, mold release agents, colorants such as red iron oxide, titanium oxide,carbon blacl~ organic color pigments such as phthalo~yanine blue or green, an~idegradal~ts, W absorbers, calcium silicate, holl~w glass or resin micro-spheres, tbicl~ening agents, inhibitors and the like. Care should be exercised lo in ~e use of high filler coIltents as this may give high viscosities and result in ~w and h~dling di~culties.
A preferred thermosetting resin-containing composition consists of a styrene con~aining modi~ed acrylic resin mixture which is sold by GenCorp I~c. under the ~rademark Genglaze~. :
1~ A pre~er~e.d reinforcing i;ber used in the i~ve~ion is glass ~ber which consis~s of conventional spun glass strand having a diame~er between S - - -~
and 50 microns and a cllt length of 1 ~o 8 cm. As is common in the industry, ~:
such glass LS sized and chopped to length and shipped "wetn in moisture proof containers to the ~ustomer. A preferred mateIial is tha~ svld by ~ens- ~
Corn~g ~iberglass (OCF) under the label 133~ :-The pre~erred molding method for practi~ng the invention is compression molding. ~ stack of sheets are layered t~ether. The stack is ~:
plaG~d in a forced air comrection oven and heated ab~ve the melti~g point of the the~noplastic resin component for less than one minute. The heated ~ `
2 5 preform is then placed in a compression mold where the tool temperature is adjusted to a temperatllre to c~ystallize the the~oplastic resin component.
S~cient pressllre is applied ~o fl~w mold the preform ~o fill ~t the mold.
~er a dwell time of preferably 30 to 6û seconds the mold is opened. As soon a~s p~ssible after opeI~ing the mold, a thermoset~ing resin-corltaining ~:
3 o compo~ellt is introduced into the mold in a~ amount sllfficieIlt $o create a l~yer rom 3 to 10 mils (0.076 to 0.254 mm) ~hick over the upper ~urface of the prefo~m. Ihe coated structure is held in the mold under pressure for a ~zime suf~cient ~o cure the the~nosetting resin-containing component. The coated structure is pen~tted to ~ol sufficiently for handling and is then removed from the mold.
PCr/lJS~2/0 Wo 93/16~56 213~2~ 6 ion mo~ding the mold must be ope f coating composition in the mold on coated. ln allother ~e of mOlding, such as iniecti~n molding~ the mold lS
insert t~e charge means~ i-e- ope}ling . Y
5 equal ~o the desired $hickness of the coatillg, to permlt in~ectlon o the i j ~ion may be made against the p~ess hiS ~ nt f rred embodime~t o~ the process of b fthetypedescribedabovecomprise g h~ ate (l'E~ fiber is precnt into a pre 10 ~reral l~yers c>f ~eprecut material, (15~ yers) are stacked tog~ther to di h~ge 'rhe m~ldiIIg charge is ~e~ p ction ~ven where the ther~nop}astic r mpli5hed ~vith ar~ air tempelature ds The ~dow (velocity) of heated ai h ge from 150 to 400 feet per minute ( i h f r au average e~ickness mold charg ~,i kness ~f the charge o~ less th~ 7 ~
A~r th~ resill is remelted, the moldlng char~e is removed nd placed ~1~ a compression mold-;cally be~wegn l5~l~5 c whe~ Usi g P Yal eSilcl The~h~rgesizeis~picallyb f the part to be rnolded hs the mold ch~ge, a tool presssure of 2000 psi (13.8 P~ pa~cals) or greater s~ould be i h i typicalb mamtained through the dll MOld dwell is typically 3~60 second P
t~ck~ess of the part-IJpon completion of ~he part fo~g step, sU~a~e ment is achieved through use of in t~osett1ng~es~-co~ n terial Asdisclosedabove~thecoatl g b~ done ~alwally or by aUtomate al operatio~, the mold halVeS are s p compledon of ehe part forming proce5s. It is essential at this stage that the ld d part be ~ee of debris~ e-~- mldiIlg d ~ ith a catalyst amd then poured 3 5 be coated. 'rhe amount Df coating used is typically 0-06 to 0~2 grams per (0 0093 to 0 0341 gm/sqcm) of part sur W~ 93/16~6 PC~/US92/01391 7 2 1 31)12() will give a co~i~ thichless from 3 ~o 10 mils (0.076 to 0.254 mm). The mold - is then closed, and a tool pressure of not more ~han 1000 psi (6.9 M pascals), S0~00 psi is optimal, (3.5 M - S.S M pascals~ is achieved. This tool pressure flows the in-mold coating over the surface of the molded part. The mold 5 dwell is 1S-60 seconds depending on the particular coating system used. The mold is then opened, and the part is removed.
'rhe composite part can be assembled w~th steel par~s ar~d paint~d using well kn~wn procedures. Among the many su~table paint ~ ~
compositions which may be used are those disclosed i~ U.S. Patents : ~:
Io 4,816950û, U.S.4,gS4,559 and U.S.5,051,209. .
In the a~ltomated process, upon completion of ~he part forming step, the pressure is relieved, and the mold halves are separated slightly.
Precatalyzed coating composition is then injected through an injector port across the surface of the ~ool. Ag~ the same rule for the amol~nt ~f coating 15 applies. Immediately after~jection, the mold is closed to-a ~ool pressure of not more thaII 1000 psi ~.9 M pascals), and ~he- mold dwell time ;s again 1~- :
60 seconds dependLIlg on the particular ~pe of coating composition used.
I'he lmold is then opened and the part removed.
The process of the invention can be used to mold automobile 2 ~ parts such as ~e and headlamp assemblies, deck hoods, ~enders9 door pane}s and roofs as well as in the maIIufacture of various plastic articles suchas food trays~ appliance and e!ec~cal components and in other ~pplications where surface smoothness is required ~or subsequent application o paint.
The in-mold-coated produc~s of this inve~tio~ are re~ycla~le.
2 5 The proper~ies of recovered thermoplastic products are not adversely af~cted by ~he presence of the the~mosetting resin-co~t~g coatings.
The invention will be further illustrated by the following examples in which parts and percentages are by weight unless otherwise irldicate~ Units reported throughout the specifica~ion and claims in SI units 3 o hav~ been converted from the English system to the SI System.
EXAMPLES
E~MPLE 1 A sel~-supporting porous batt was prepared from polyethylene tereph~halate f;ber (PET) having an as spun denier of 1.5. The ~lber was 3 5 coverted to a staple length of 1/4 inch (0.635 cm) and intimately mixed with I
inch long glass ~lber having a diameter of about 0.5 mil (0.013 mm). The wo 93/16856 P~/US92/01391 2l3~12 ~; t 8 above ingredients were slurried in water and directed to a ~nng belt ~rom a paper machine head box, then to a dryer. The mat co~sisted of 40.7 Wt> %
glass fiber (C)wens Cor~ g Fiberglass '~' ) $7.2 Wt. ~o PET fiber and 9.1 W~. % of a l~wer melting copolyester binder fiber Ci~a Geigy's antio~idant, 5 Irgan~x~1010, was added to $he slurry in an amount of 1.0 Wt. %. A belt speed of 22 fpm ~6.71 ~pm) a~d heater temperature of 195C was used to partially melt dle PEI fiber. A batt having a basis wei~ht of about 0.171 -l~/sqft ~8.35 lcq/sqcm) aIld a consistency of 0.54 Wt~ % was obtained.
The batt was placed in a convecSion ove~ d heated at a 0 temper2ture of 285C for 30 secoIlds while circulating hot ~ ~hrough the batt ~t ab~ut 350 ~eet per miD:ute (106.68 m~min) to melt the PE~T
componellt. The batt was then placed iIl a compressioIl mold for 1 mi~ute at a temperature of 15~180C to crystallize the structure. ~Iold pressure was co~tr~lled a~ betweell 1,500 and 2,500 psi (1034 and 17.2~ ~ pascals). The 5 mold was ope~ed to ~xpose the ex~erior s~ ce of ~Ihe ~nol~d stNct~e.
As soo~ as possible after ~pening ~e ~old, a theImosetti~g s~e~e containi~g ~odified acrylic res~nous coating matenal sold by Ger~Cor,o Lnc. under the trademark GENGIAZE 0~EC 600 was applied to the exposed surface of tbe moldod stn~cntre in all amount of 0.14 o ~amjsqu~re inch (217.95 ~n/sqm) The m~d was reclosed uIIder partial vacuum at a lower pressuro of abost ~00 to lO00 psi 11.4 to 6.9 M pascals) to distnbute dle coating ~atenal ~ver ~he surface ~f the molded s~uc~ure.
~er 60 secoIIds, ~e mold was opened and the coated structure was re~noved. T~e coa~g was mliforrnly distributedl haviDg a thiclcness of 6 2~ ~i~ls~ ~i~ a very smooth surace The p~ocedure described in Examp1e 1 was repe~ted except tha~ ~he glass ~ber content of the bat~ was reduced to 25 wt. ~o, no binder f~ was used, the polyethylene terephthalate fiber conteDt was increased to 3 o 75 wt, % and Ciba Geigy's ~mDoxidaDt, Irgano~1330, was used in am amolmt of 0.25 wt. %, the belt speed was increased to 25 l~pm (7.62 m/m) and the heater temperatnre was increased to 280C. The sheet, ha~ling a basis weight of 0 0~ lb/sqft (0.444 kg/s4m) A clicker die was used to convert the rolled batt into a f~rm 35 suitable for thermal compression molding. Aprefolm consisting of twenty : I
WO ~3/~685~ PCr/l~S92/01393 9 ~130120 (2û~ sheets stacked as a batt ga~e a part weight of abou~ 1.0 to 1.5 lbs/sqft (0.488 to 0.732 ~n/sqcm) on thermal compression molding. :
Be~ore thermal compression molding, the batt was placed in a collvection oven and hot air was circulated through the batt at about 350 ft/~ (106.68 m~min) ~or 30 secoIlds at 28~QC to convert the porous b~tt ~ -into a moldable form. The pliable melt was placed into a mold ~or orle mimlte at a mold ~emperature of l50 to 180C to produce a crystallized stmctllre. The mold pressure was controlled at 2000 psi (13.8 M pascals).
As soon as possible afte} opeI~ing the mold, a resinous coatillg 0 mateFial consis~ing of GENGI~ZE~ EC 600 was applied to the exposed surface ~ ~he molded struc~ure in an amount of 0.14 grams/s~q inch (217.95 F~f sq,m). The mold was reclosed under partial vacuum at a lower pressure of about 200 ~o lQ00 psi (1.4 to 6.9 M pascals) t~ distribu~e the coating material over the surface of the molded structure. After 60 sec~nds the mold w~ opened, a~d the coated structure was removed. The coating had a ~hic~ess of 6 mils (0.1521rlm) A very smoo~h coated sur~ace was obtai~ed.
Products prepared by ~e process of this invention were tested USillg a BeIldix Surface Pro~lometer, ~vlodel No. 21, stylus head BendL~ T-231 and probe diameter of 0.0~)4 inch (0 ~1016 mm) to determine the sl:lrace o r~ughness. Produc~s of ~his invention were found to have a maximum surface rou~hness de~nation of less ~h~ 50 micro-inches ~0.00127 mm) ~ver a 0.25 inch (635 mm) span.
Adhesion of the thermosetting resin-contaiI~ing coating ~o the ~heImoplasti:c substrate was tested USiIlg an Ins~ron tensile ~ester. Two metal ~5 ~ylinders h~ving a diameter ~ 1.596 inches (4.~5 cm~,2 sq inches sll~face area,(l2.9 sqcm) were bonded using Dexter H)fsol~ adhesi~e, EA 934NA, a two part past adhesive, to each side of a test sample. When the adhesive was cured, the pieces we~e pulled ~part in the Instron tester. 7~he test samples were pr~pared b~ the process described in the Examples. ~he resul~s of ~he 3 0 - tests~é set forth in the follo~ving Table:
wC~ 93/168~6 P~r/lJSg2~01391 2131~12 lO
MA'rERI.4L STRENG~ ~YP~ OF FAILURE
(psi) SM pascals) S~nple 1 2452 16.9 Coatingseparatedfrom the subs~rate ~ample 2 2379 16.4 Coa~ g separa~ed from the substrate Sample 3 2810 19.4 Del~nination of the substrate 0 Sample 4 ~80 17.1 Delamination of the ~Pai~ed) Substrate For pu~poses of defining this inve~tion, the term "~dhesion va. lue means the tensile s~rength of the bo~d between the surface coating and the substrate as measllred using an Instron tensile tester, Model ~o.1:1~7, using a ~,~0 kg reversible load cell, or equivalent, and reported in psi ~pascals). Products of ~is inven~ion have adhesion values greater than 1000 psi ~69 M pascals). This adhesion value must be at~ained to provide an acceptable prodllct w~ich is useful in industry a~plicatio~s. In conducting 2 o ~es~s ~o d~ermine adhesion values any Sllit2ble adhesive which has a bondingstre~g~h greater than the force reql~i} ed ~o delami~ate the substrate may be used.
. ~, , , , , , ~ , ,~",; , ,"; ~ ," ,;_,, ,,,,,_ , _,__ ~ " r _,_ ~ _ ___ _ ,,~, j, ~ ",~""",, ,~",~"";~ .r~
A~r th~ resill is remelted, the moldlng char~e is removed nd placed ~1~ a compression mold-;cally be~wegn l5~l~5 c whe~ Usi g P Yal eSilcl The~h~rgesizeis~picallyb f the part to be rnolded hs the mold ch~ge, a tool presssure of 2000 psi (13.8 P~ pa~cals) or greater s~ould be i h i typicalb mamtained through the dll MOld dwell is typically 3~60 second P
t~ck~ess of the part-IJpon completion of ~he part fo~g step, sU~a~e ment is achieved through use of in t~osett1ng~es~-co~ n terial Asdisclosedabove~thecoatl g b~ done ~alwally or by aUtomate al operatio~, the mold halVeS are s p compledon of ehe part forming proce5s. It is essential at this stage that the ld d part be ~ee of debris~ e-~- mldiIlg d ~ ith a catalyst amd then poured 3 5 be coated. 'rhe amount Df coating used is typically 0-06 to 0~2 grams per (0 0093 to 0 0341 gm/sqcm) of part sur W~ 93/16~6 PC~/US92/01391 7 2 1 31)12() will give a co~i~ thichless from 3 ~o 10 mils (0.076 to 0.254 mm). The mold - is then closed, and a tool pressure of not more ~han 1000 psi (6.9 M pascals), S0~00 psi is optimal, (3.5 M - S.S M pascals~ is achieved. This tool pressure flows the in-mold coating over the surface of the molded part. The mold 5 dwell is 1S-60 seconds depending on the particular coating system used. The mold is then opened, and the part is removed.
'rhe composite part can be assembled w~th steel par~s ar~d paint~d using well kn~wn procedures. Among the many su~table paint ~ ~
compositions which may be used are those disclosed i~ U.S. Patents : ~:
Io 4,816950û, U.S.4,gS4,559 and U.S.5,051,209. .
In the a~ltomated process, upon completion of ~he part forming step, the pressure is relieved, and the mold halves are separated slightly.
Precatalyzed coating composition is then injected through an injector port across the surface of the ~ool. Ag~ the same rule for the amol~nt ~f coating 15 applies. Immediately after~jection, the mold is closed to-a ~ool pressure of not more thaII 1000 psi ~.9 M pascals), and ~he- mold dwell time ;s again 1~- :
60 seconds dependLIlg on the particular ~pe of coating composition used.
I'he lmold is then opened and the part removed.
The process of the invention can be used to mold automobile 2 ~ parts such as ~e and headlamp assemblies, deck hoods, ~enders9 door pane}s and roofs as well as in the maIIufacture of various plastic articles suchas food trays~ appliance and e!ec~cal components and in other ~pplications where surface smoothness is required ~or subsequent application o paint.
The in-mold-coated produc~s of this inve~tio~ are re~ycla~le.
2 5 The proper~ies of recovered thermoplastic products are not adversely af~cted by ~he presence of the the~mosetting resin-co~t~g coatings.
The invention will be further illustrated by the following examples in which parts and percentages are by weight unless otherwise irldicate~ Units reported throughout the specifica~ion and claims in SI units 3 o hav~ been converted from the English system to the SI System.
EXAMPLES
E~MPLE 1 A sel~-supporting porous batt was prepared from polyethylene tereph~halate f;ber (PET) having an as spun denier of 1.5. The ~lber was 3 5 coverted to a staple length of 1/4 inch (0.635 cm) and intimately mixed with I
inch long glass ~lber having a diameter of about 0.5 mil (0.013 mm). The wo 93/16856 P~/US92/01391 2l3~12 ~; t 8 above ingredients were slurried in water and directed to a ~nng belt ~rom a paper machine head box, then to a dryer. The mat co~sisted of 40.7 Wt> %
glass fiber (C)wens Cor~ g Fiberglass '~' ) $7.2 Wt. ~o PET fiber and 9.1 W~. % of a l~wer melting copolyester binder fiber Ci~a Geigy's antio~idant, 5 Irgan~x~1010, was added to $he slurry in an amount of 1.0 Wt. %. A belt speed of 22 fpm ~6.71 ~pm) a~d heater temperature of 195C was used to partially melt dle PEI fiber. A batt having a basis wei~ht of about 0.171 -l~/sqft ~8.35 lcq/sqcm) aIld a consistency of 0.54 Wt~ % was obtained.
The batt was placed in a convecSion ove~ d heated at a 0 temper2ture of 285C for 30 secoIlds while circulating hot ~ ~hrough the batt ~t ab~ut 350 ~eet per miD:ute (106.68 m~min) to melt the PE~T
componellt. The batt was then placed iIl a compressioIl mold for 1 mi~ute at a temperature of 15~180C to crystallize the structure. ~Iold pressure was co~tr~lled a~ betweell 1,500 and 2,500 psi (1034 and 17.2~ ~ pascals). The 5 mold was ope~ed to ~xpose the ex~erior s~ ce of ~Ihe ~nol~d stNct~e.
As soo~ as possible after ~pening ~e ~old, a theImosetti~g s~e~e containi~g ~odified acrylic res~nous coating matenal sold by Ger~Cor,o Lnc. under the trademark GENGIAZE 0~EC 600 was applied to the exposed surface of tbe moldod stn~cntre in all amount of 0.14 o ~amjsqu~re inch (217.95 ~n/sqm) The m~d was reclosed uIIder partial vacuum at a lower pressuro of abost ~00 to lO00 psi 11.4 to 6.9 M pascals) to distnbute dle coating ~atenal ~ver ~he surface ~f the molded s~uc~ure.
~er 60 secoIIds, ~e mold was opened and the coated structure was re~noved. T~e coa~g was mliforrnly distributedl haviDg a thiclcness of 6 2~ ~i~ls~ ~i~ a very smooth surace The p~ocedure described in Examp1e 1 was repe~ted except tha~ ~he glass ~ber content of the bat~ was reduced to 25 wt. ~o, no binder f~ was used, the polyethylene terephthalate fiber conteDt was increased to 3 o 75 wt, % and Ciba Geigy's ~mDoxidaDt, Irgano~1330, was used in am amolmt of 0.25 wt. %, the belt speed was increased to 25 l~pm (7.62 m/m) and the heater temperatnre was increased to 280C. The sheet, ha~ling a basis weight of 0 0~ lb/sqft (0.444 kg/s4m) A clicker die was used to convert the rolled batt into a f~rm 35 suitable for thermal compression molding. Aprefolm consisting of twenty : I
WO ~3/~685~ PCr/l~S92/01393 9 ~130120 (2û~ sheets stacked as a batt ga~e a part weight of abou~ 1.0 to 1.5 lbs/sqft (0.488 to 0.732 ~n/sqcm) on thermal compression molding. :
Be~ore thermal compression molding, the batt was placed in a collvection oven and hot air was circulated through the batt at about 350 ft/~ (106.68 m~min) ~or 30 secoIlds at 28~QC to convert the porous b~tt ~ -into a moldable form. The pliable melt was placed into a mold ~or orle mimlte at a mold ~emperature of l50 to 180C to produce a crystallized stmctllre. The mold pressure was controlled at 2000 psi (13.8 M pascals).
As soon as possible afte} opeI~ing the mold, a resinous coatillg 0 mateFial consis~ing of GENGI~ZE~ EC 600 was applied to the exposed surface ~ ~he molded struc~ure in an amount of 0.14 grams/s~q inch (217.95 F~f sq,m). The mold was reclosed under partial vacuum at a lower pressure of about 200 ~o lQ00 psi (1.4 to 6.9 M pascals) t~ distribu~e the coating material over the surface of the molded structure. After 60 sec~nds the mold w~ opened, a~d the coated structure was removed. The coating had a ~hic~ess of 6 mils (0.1521rlm) A very smoo~h coated sur~ace was obtai~ed.
Products prepared by ~e process of this invention were tested USillg a BeIldix Surface Pro~lometer, ~vlodel No. 21, stylus head BendL~ T-231 and probe diameter of 0.0~)4 inch (0 ~1016 mm) to determine the sl:lrace o r~ughness. Produc~s of ~his invention were found to have a maximum surface rou~hness de~nation of less ~h~ 50 micro-inches ~0.00127 mm) ~ver a 0.25 inch (635 mm) span.
Adhesion of the thermosetting resin-contaiI~ing coating ~o the ~heImoplasti:c substrate was tested USiIlg an Ins~ron tensile ~ester. Two metal ~5 ~ylinders h~ving a diameter ~ 1.596 inches (4.~5 cm~,2 sq inches sll~face area,(l2.9 sqcm) were bonded using Dexter H)fsol~ adhesi~e, EA 934NA, a two part past adhesive, to each side of a test sample. When the adhesive was cured, the pieces we~e pulled ~part in the Instron tester. 7~he test samples were pr~pared b~ the process described in the Examples. ~he resul~s of ~he 3 0 - tests~é set forth in the follo~ving Table:
wC~ 93/168~6 P~r/lJSg2~01391 2131~12 lO
MA'rERI.4L STRENG~ ~YP~ OF FAILURE
(psi) SM pascals) S~nple 1 2452 16.9 Coatingseparatedfrom the subs~rate ~ample 2 2379 16.4 Coa~ g separa~ed from the substrate Sample 3 2810 19.4 Del~nination of the substrate 0 Sample 4 ~80 17.1 Delamination of the ~Pai~ed) Substrate For pu~poses of defining this inve~tion, the term "~dhesion va. lue means the tensile s~rength of the bo~d between the surface coating and the substrate as measllred using an Instron tensile tester, Model ~o.1:1~7, using a ~,~0 kg reversible load cell, or equivalent, and reported in psi ~pascals). Products of ~is inven~ion have adhesion values greater than 1000 psi ~69 M pascals). This adhesion value must be at~ained to provide an acceptable prodllct w~ich is useful in industry a~plicatio~s. In conducting 2 o ~es~s ~o d~ermine adhesion values any Sllit2ble adhesive which has a bondingstre~g~h greater than the force reql~i} ed ~o delami~ate the substrate may be used.
. ~, , , , , , ~ , ,~",; , ,"; ~ ," ,;_,, ,,,,,_ , _,__ ~ " r _,_ ~ _ ___ _ ,,~, j, ~ ",~""",, ,~",~"";~ .r~
Claims (10)
1. A process for preparing a recyclable reinforced composite structure having enhanced surface appearance comprising a) heating a batt comprised of a plurality of layers of a self-supporting porous web comprised of randomly dispersed high modulus reinforcing fiber held together by solidified thermoplastic resin to convert the batt into a moldable form;
b) placing the moldable form into a heated mold and flowing said moldable form under pressure to substantially crystallize the thermoplastic resin component, c) introducing a thermosetting resin-containing coating material into the mold adjacent at least one surface of the crystallized structure by separating the sections of said mold and/or releasing the pressure and closing said heated mold under pressure to provide a substantially uniform coating on said one surface, d) dwelling the coated structure in the mold for a time sufficient to set said coating material, and e) recovering a molded part having an enhanced surface appearance.
b) placing the moldable form into a heated mold and flowing said moldable form under pressure to substantially crystallize the thermoplastic resin component, c) introducing a thermosetting resin-containing coating material into the mold adjacent at least one surface of the crystallized structure by separating the sections of said mold and/or releasing the pressure and closing said heated mold under pressure to provide a substantially uniform coating on said one surface, d) dwelling the coated structure in the mold for a time sufficient to set said coating material, and e) recovering a molded part having an enhanced surface appearance.
2. The process of Claim 1 wherein said thermoplastic resin is a polyester.
3. The process of Claim 1 wherein said high modulus reinforcing fiber is glass fiber comprising from 5 to 50 by weight of said moldable form.
4. The process of Claim 3 wherein said glass fiber has a length from 1 to 10 cm and a diameter from 5 to 50 microns and said thermoplastic resin is polyethylene terephthalate.
5. A composite structure having a substrate comprised of high modulus reinforcing fibers randomly dispersed in a thermoplastic resin and a thin thermosetting resin-containing coating adhered to a surface of said substrate, said thermoplastic resin being in a substantially crystallized state,said coating having a very smooth surface and adherring tenaciously to the surface of said substrate.
6. A composite structure having a substrate comprised of high modulus reinforcing fibers randomly dispersed in a thermoplastic resin and a thin thermosetting resin-containing coating adhered to a surface of said substrate, said thermoplastic resin being a substantially crystallized state, said coating having a maximum surface roughness deviation of less than 50 micro-inches (0.00127 mm) over a 0.25 inch (6.35mm) span for the coated surface and a coating to substrate adhesion value greater than 1000 psi (6.9 M pascals).
7. The structure of Claim 6 wherein said coating has a thickness from about 0.076 to 0.26 mm.
8. The structure of Claim 7 wherein said reinforcing fiber is glass fiber and said thermoplastic resin is a polyester resin.
9. The structure of Claim 8 wherein said thermosetting resin is an acrylic based vinyl polymer composition.
10. The structure of Claim 8 having multiple layers of paint on the surface of said thin thermosetting resin-containing coating.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1992/001391 WO1993016856A1 (en) | 1992-02-21 | 1992-02-21 | Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2130120A1 true CA2130120A1 (en) | 1993-09-02 |
Family
ID=39015693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2130120 Abandoned CA2130120A1 (en) | 1992-02-21 | 1992-02-21 | Recyclable molded high modulus fiber reinforced thermoplastic structures and process for preparing the same |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5632949A (en) |
| EP (1) | EP0626901B1 (en) |
| JP (1) | JPH07503912A (en) |
| AU (1) | AU2014092A (en) |
| BR (1) | BR9207085A (en) |
| CA (1) | CA2130120A1 (en) |
| CZ (1) | CZ9402000A3 (en) |
| DE (1) | DE69223806T2 (en) |
| ES (1) | ES2111069T3 (en) |
| WO (1) | WO1993016856A1 (en) |
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| JPH08174688A (en) * | 1994-12-21 | 1996-07-09 | Ikeda Bussan Co Ltd | Resin molded form for vehicle |
| EP0933195A1 (en) * | 1997-12-17 | 1999-08-04 | Freistaat Bayern, vertreten durch Friedrich-Alexander-Universität Erlangen-Nürnberg | Fibre-reinforced synthetic structure |
| US20030090035A1 (en) * | 2000-04-20 | 2003-05-15 | Mori Steven J. | Method of molding a panel |
| US6617033B1 (en) | 2000-07-12 | 2003-09-09 | Omnova Solutions Inc. | Method for in-mold coating a polyolefin article |
| US6793861B2 (en) | 2000-07-12 | 2004-09-21 | Omnova Solutions Inc. | Optimization of in-mold coating injection molded thermoplastic substrates |
| US20040071980A1 (en) * | 2000-07-12 | 2004-04-15 | Mcbain Douglas S. | Method for in-mold coating a polyolefin article |
| US7105231B2 (en) * | 2001-10-22 | 2006-09-12 | Omnova Solutions Inc. | In-mold coating barrier for a substrate injection orifice |
| US6890469B2 (en) | 2001-10-22 | 2005-05-10 | Omnova Solutions Inc. | Selectively controlling in-mold coating flow |
| US7045213B2 (en) * | 2001-10-22 | 2006-05-16 | Omnova Solutions Inc. | In-mold coating injection inlet flow control |
| US6887550B2 (en) * | 2001-10-22 | 2005-05-03 | Omnova Solutions Inc. | Removable defined flange for in-mold coating containment |
| US6676877B2 (en) | 2002-04-03 | 2004-01-13 | Omnova Solutions Inc. | Mold runner for prevention of in-mold coating flow |
| US20040121034A1 (en) * | 2002-12-10 | 2004-06-24 | Mcbain Douglas S. | Integral injection molding and in-mold coating apparatus |
| US20050266757A1 (en) * | 2003-10-17 | 2005-12-01 | Roekens Bertrand J | Static free wet use chopped strands (WUCS) for use in a dry laid process |
| US20050156351A1 (en) * | 2004-01-20 | 2005-07-21 | Omnova Solutions, Inc. | Apparatus and method for in-mold coating an article by injecting an in-mold coating through the article |
| US7279059B2 (en) * | 2004-12-28 | 2007-10-09 | Owens Corning Intellectual Capital, Llc | Polymer/WUCS mat for use in automotive applications |
| US7252729B2 (en) * | 2004-12-29 | 2007-08-07 | Owens-Corning Fiberglas Technology Inc. | Polymer/WUCS mat for use in sheet molding compounds |
| US8652288B2 (en) * | 2006-08-29 | 2014-02-18 | Ocv Intellectual Capital, Llc | Reinforced acoustical material having high strength, high modulus properties |
| US20100143692A1 (en) * | 2008-12-10 | 2010-06-10 | Ryan James P | Carbon and Glass Fiber Reinforced Composition |
| US20140221553A1 (en) * | 2013-02-07 | 2014-08-07 | Holland Composites Innovation B.V. | Composite materials and shaped articles |
| JP5767415B1 (en) * | 2013-08-13 | 2015-08-19 | 帝人株式会社 | Decorative molded product manufacturing method and decorative molded product |
| JP6215889B2 (en) * | 2015-10-14 | 2017-10-18 | 株式会社タカギセイコー | Composite molding system |
| JP6884650B2 (en) * | 2017-06-22 | 2021-06-09 | 三菱重工業株式会社 | Method of manufacturing composite structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4081578A (en) * | 1974-06-27 | 1978-03-28 | The General Tire & Rubber Company | In-mold coating composition and method of applying same |
| CA1133167A (en) * | 1978-06-08 | 1982-10-05 | Joseph Feltzin | In-mold coating compositions containing functional group terminated liquid polymers |
| US4189517A (en) * | 1978-11-08 | 1980-02-19 | The General Tire & Rubber Company | Low-shrink in-mold coating |
| US4239796A (en) * | 1979-06-21 | 1980-12-16 | The General Tire & Rubber Company | In-mold coating of structural foams and resultant product |
| US4457797A (en) * | 1982-03-08 | 1984-07-03 | E. I. Dupont De Nemours And Company | Process for thermoforming reinforced polymer sheets |
| GB2119282B (en) * | 1982-04-26 | 1985-08-29 | Great Lakes Carbon Corp | Coated fiber-reinforced body and method of making |
| US4716072A (en) * | 1986-12-29 | 1987-12-29 | General Electric Company | Multilayer composite structure for smooth surfaces |
| US4737403A (en) * | 1987-04-03 | 1988-04-12 | Ppg Industries, Inc. | Method of coating fiber-reinforced plastic substrates |
| US4948661A (en) * | 1987-07-10 | 1990-08-14 | C. H. Masland & Sons | Glossy finish fiber reinforced molded product and processes of construction |
| US4781876A (en) * | 1987-07-16 | 1988-11-01 | General Motors Corporation | Method of producing glass fiber mat reinforced plastic panels |
| JPH01198314A (en) * | 1988-02-03 | 1989-08-09 | Honda Motor Co Ltd | Method and apparatus for preparing composite molded object |
| JPH01318045A (en) * | 1988-05-10 | 1989-12-22 | E I Du Pont De Nemours & Co | Composite material composed of wet molding mixture of glass fiber and thermoplastic fiber |
| US5021297A (en) * | 1988-12-02 | 1991-06-04 | Ppg Industries, Inc. | Process for coating plastic substrates with powder coating compositions |
| US5009821A (en) * | 1989-02-23 | 1991-04-23 | Libbey-Owens-Ford Co. | Molding method for eliminating fiber readout |
| US4983247A (en) * | 1989-08-07 | 1991-01-08 | General Electric Company | Method for producing resin rich surface layer on composite thermoplastic material |
| US5134016A (en) * | 1990-10-31 | 1992-07-28 | E. I. Du Pont De Nemours And Company | Fiber reinforced porous sheets |
-
1992
- 1992-02-21 JP JP5514782A patent/JPH07503912A/en active Pending
- 1992-02-21 EP EP19920912089 patent/EP0626901B1/en not_active Expired - Lifetime
- 1992-02-21 BR BR9207085A patent/BR9207085A/en not_active IP Right Cessation
- 1992-02-21 AU AU20140/92A patent/AU2014092A/en not_active Abandoned
- 1992-02-21 CZ CZ942000A patent/CZ9402000A3/en unknown
- 1992-02-21 WO PCT/US1992/001391 patent/WO1993016856A1/en not_active Application Discontinuation
- 1992-02-21 CA CA 2130120 patent/CA2130120A1/en not_active Abandoned
- 1992-02-21 DE DE1992623806 patent/DE69223806T2/en not_active Expired - Fee Related
- 1992-02-21 ES ES92912089T patent/ES2111069T3/en not_active Expired - Lifetime
-
1996
- 1996-01-24 US US08/590,959 patent/US5632949A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5632949A (en) | 1997-05-27 |
| DE69223806T2 (en) | 1998-07-23 |
| AU2014092A (en) | 1993-09-13 |
| CZ9402000A3 (en) | 1994-12-15 |
| EP0626901B1 (en) | 1997-12-29 |
| ES2111069T3 (en) | 1998-03-01 |
| BR9207085A (en) | 1995-12-12 |
| EP0626901A1 (en) | 1994-12-07 |
| WO1993016856A1 (en) | 1993-09-02 |
| DE69223806D1 (en) | 1998-02-05 |
| JPH07503912A (en) | 1995-04-27 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |