US20050095415A1 - Glass mat thermoplastic composite - Google Patents
Glass mat thermoplastic composite Download PDFInfo
- Publication number
- US20050095415A1 US20050095415A1 US10/696,869 US69686903A US2005095415A1 US 20050095415 A1 US20050095415 A1 US 20050095415A1 US 69686903 A US69686903 A US 69686903A US 2005095415 A1 US2005095415 A1 US 2005095415A1
- Authority
- US
- United States
- Prior art keywords
- laminate material
- fiber reinforced
- layer
- reinforced laminate
- composition
- 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
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000011521 glass Substances 0.000 title claims abstract description 22
- 229920001169 thermoplastic Polymers 0.000 title claims description 13
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 10
- 239000000835 fiber Substances 0.000 claims abstract description 74
- 239000002648 laminated material Substances 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 49
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 230000006835 compression Effects 0.000 claims abstract description 9
- 238000007906 compression Methods 0.000 claims abstract description 9
- 239000003365 glass fiber Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000012466 permeate Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 30
- 229920002601 oligoester Polymers 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 21
- -1 accelerators Substances 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 15
- 239000011324 bead Substances 0.000 claims description 14
- 239000012985 polymerization agent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229920000515 polycarbonate Polymers 0.000 claims description 11
- 239000004417 polycarbonate Substances 0.000 claims description 11
- 239000002274 desiccant Substances 0.000 claims description 10
- 230000003014 reinforcing effect Effects 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 238000005809 transesterification reaction Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004606 Fillers/Extenders Substances 0.000 claims description 7
- 239000004609 Impact Modifier Substances 0.000 claims description 7
- 239000012963 UV stabilizer Substances 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 239000004599 antimicrobial Substances 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- 235000019241 carbon black Nutrition 0.000 claims description 7
- 239000003086 colorant Substances 0.000 claims description 7
- 238000000748 compression moulding Methods 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- 239000003017 thermal stabilizer Substances 0.000 claims description 7
- 238000003856 thermoforming Methods 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 229920001296 polysiloxane Chemical class 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000001993 wax Substances 0.000 claims description 5
- 239000004971 Cross linker Substances 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 4
- 229920001281 polyalkylene Polymers 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000013638 trimer Substances 0.000 claims description 4
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- NMYFVWYGKGVPIW-UHFFFAOYSA-N 3,7-dioxabicyclo[7.2.2]trideca-1(11),9,12-triene-2,8-dione Chemical compound O=C1OCCCOC(=O)C2=CC=C1C=C2 NMYFVWYGKGVPIW-UHFFFAOYSA-N 0.000 claims description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 2
- PCXMISPZSFODLD-UHFFFAOYSA-N 6,9-dioxatricyclo[9.3.1.14,14]hexadeca-1(14),2,4(16),11(15),12-pentaene-5,10-dione Chemical compound C1=C(C=C2)C(=O)OCCOC(=O)C3=CC=C1C2=C3 PCXMISPZSFODLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 125000005609 naphthenate group Chemical group 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 5
- 229920000554 ionomer Polymers 0.000 claims 2
- 229920000058 polyacrylate Polymers 0.000 claims 2
- 229920001225 polyester resin Polymers 0.000 claims 2
- 239000004645 polyester resin Substances 0.000 claims 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims 2
- 229920000098 polyolefin Polymers 0.000 claims 2
- 229920001897 terpolymer Polymers 0.000 claims 2
- 229920002943 EPDM rubber Polymers 0.000 claims 1
- 238000010030 laminating Methods 0.000 claims 1
- 238000013508 migration Methods 0.000 claims 1
- 230000005012 migration Effects 0.000 claims 1
- 229920006344 thermoplastic copolyester Polymers 0.000 claims 1
- 229920002725 thermoplastic elastomer Polymers 0.000 claims 1
- 229920002397 thermoplastic olefin Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 71
- 239000000463 material Substances 0.000 description 9
- 229920005668 polycarbonate resin Polymers 0.000 description 7
- 239000004431 polycarbonate resin Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000003733 fiber-reinforced composite Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010107 reaction injection moulding Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- BAFNLNDNPBJCKT-UHFFFAOYSA-N 2,2,7,7-tetrabutyl-1,3,6,8,2,7-tetraoxadistannecane Chemical compound CCCC[Sn]1(CCCC)OCCO[Sn](CCCC)(CCCC)OCCO1 BAFNLNDNPBJCKT-UHFFFAOYSA-N 0.000 description 1
- COKREYXJRHTKSH-UHFFFAOYSA-N 2,2-dibutyl-1,3,2-dioxastannepane Chemical compound CCCC[Sn]1(CCCC)OCCCCO1 COKREYXJRHTKSH-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- 229920004142 LEXAN™ Polymers 0.000 description 1
- 239000004418 Lexan Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- FQYHHEJETOLDHR-UHFFFAOYSA-K butyl(chloro)tin(2+);dihydroxide Chemical compound CCCC[Sn](O)(O)Cl FQYHHEJETOLDHR-UHFFFAOYSA-K 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- XCRHYAQWBYDRGV-JXMROGBWSA-N ethyl (e)-3-(4-propan-2-ylphenyl)prop-2-enoate Chemical compound CCOC(=O)\C=C\C1=CC=C(C(C)C)C=C1 XCRHYAQWBYDRGV-JXMROGBWSA-N 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012758 reinforcing additive Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 210000000329 smooth muscle myocyte Anatomy 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DTRIEULISHKBQO-UHFFFAOYSA-N tributoxy(butyl)stannane Chemical compound CCCCO[Sn](CCCC)(OCCCC)OCCCC DTRIEULISHKBQO-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
-
- 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
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4218—Glass fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/593—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives to layered webs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/249942—Fibers are aligned substantially parallel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/249942—Fibers are aligned substantially parallel
- Y10T428/249944—Fiber is precoated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/249942—Fibers are aligned substantially parallel
- Y10T428/249946—Glass fiber
Definitions
- the present invention relates to a glass mat thermoplastic (GMT) composite, and more particularly to glass mat thermoplastic (GMT) composite having a Class-A surface made with a blend of thermoplastic resins and polymerizable moieties providing a resin rich surface finish when heated and molded using thermoforming and compression molding tools.
- GTT glass mat thermoplastic
- GMT composite A relatively inexpensive product is GMT composite.
- GMT composites can molded and stamped into a variety suitable products, most notably are bumpers.
- Previous known GMT products do not have sufficiently surface qualities to be used in visible applications on automobiles, such as body panels. The quality of the finish has to be suitable for painting, and this surface finish is designated a Class-A surface.
- SMC sheet molded compounds
- SMCs are substantially more expensive than GMT fabricated parts, and generate a lot of scrap. What is needed is a GMT that has a Class-A surface that can be used in visible, painted parts.
- Kim in U.S. Pat. No. 4,983,247, teaches a method for making a fiber reinforced composite having a resin rich first layer on the surface. Forming a fiber free layer of a thermoplastic resin, heating a composite bulk layer of resin and reinforcing fibers, and then compressing the first layer and the composite bulk layer, so that the heat from the bulk layer causes the first layer to melt.
- Fitzgibbon in U.S. Pat. No. 5,464,585, teaches a method where a resin-modifying auxiliary material is concentrated in the surface portion of an article.
- the method is particularly suited to RIM (reaction injection molding).
- RIM reaction injection molding
- the mold is filled with a gradient of a bulk material and an auxiliary material, where the auxiliary material is generally defined as producing superior results as a mold surface material.
- the ratio is varied with time, so that as the mold is filled there is less of the auxiliary material.
- Cited along with resin-modifying auxiliary materials are a catalyst and catalyst/initiator for polymerization, wherein they are concentrated at the surface of the mold.
- Della Vecchia et al in U.S. Pat. No. 4,612,238, discloses a process for producing a laminate that combines a layer of resin, a glass mat, another layer of resin, a second glass mat, and a third layer of resin.
- the first and third layers of resin which are thermoplastic materials, can be selected so as to obtain the desired properties.
- Various quantities of reinforcing materials, fillers and additives can be in selected proportions.
- the invention is a method for manufacturing and composition of a fiber reinforced laminate material of a multi-layered laminate having two or more layers, wherein following heating and compression molding or thermoforming the laminate material forms a composite having a Class-A surface that is resin rich.
- the fiber reinforced laminate material is typically utilized to make GMT composites that have a Class-A surface.
- the fiber reinforced laminate material is a multi-layered laminate that is formed with two or more layers, comprising: a layer comprised of a thermoplastic resin; a layer comprised of a polymerizable component comprised of chemically reactive components; and/or a layer of reinforcing fibers.
- the layers can be combined such that there is at least one layer of reinforcing fibers and a layer of a thermoplastic resin (A laminate), or at least one layer of reinforcing fibers and a layer of a polymerizable component (B laminate).
- the A laminate can in a subsequent coating, or simultaneously, be extrusion coated with a layer of the polymerizable component forming a three layer laminate (C laminate).
- the B laminate can in a subsequent coating, or simultaneously, be extrusion coated with a layer of the thermoplastic resin, which therein forms a three layer laminate that is also the C laminate. It obviously follows that the multi-layered laminates can be other combinations of the at least two layer laminate.
- thermoplastic resin layer is further comprised of a polymerization agent selected from the group consisting of initiators, accelerators, cross-linkers, catalysts, drying agents, and a combination thereof.
- the polymerization agent need not be equally distributed throughout the thermoplastic resin, but can be added as a coating to the layer of thermoplastic resin.
- the polymerizable component layer and the thermoplastic resin layer are preferably separated by the layer of reinforcing fibers.
- the polymerizable component contains chemically reactive compounds selected from the group consisting of low molecular weight polymers, macrocyclic oligomers, oligomers, prepolymers, monomers, dimers, trimers, tetramers and the like, or any combination thereof.
- the polymerizable component can be further comprised of a thermoplastic polymer, such as the thermoplastic resin.
- the reinforced fiber layer is comprised of fibers selected from the group consisting of glass fibers, metal fibers, ceramic fibers, carbon fibers, aramid fibers, synthetic polymers made from polymers such as polyester, polypropylene, polyamides, polyimides, and polyurethanes, and blends of combinations thereof.
- the fibers can be chopped, matted, picked, bonded, woven, and other wised processed to optimize handling, saturation, cost, strength and orientation.
- the thermoplastic layer is extruded onto a first side of the layer of reinforcing fibers, and the polymerizable component layer is extruded onto the opposing side of the reinforcing fiber layer.
- the chemically reactive compounds and the polymerization agents are selected so that when heated, the chemically reactive compounds polymerize forming a Class-A surface finish.
- the reinforcing fiber layer is selected so as to impart strength to the laminate following B-stage processing.
- At least one A laminate is combined with the polymerizable component or the C laminate in a thermoforming or compression molding process, wherein the laminates are heated and molded under compression.
- the laminates are combined such that the polymerizable component is sandwiched by the reinforcing fiber layers.
- the reinforcing fiber layer is further selected to be sufficiently open as to be permeable to impregnation/saturation by the thermoplastic resin, and to enable the permeation of the chemically reactive components, when the laminate is under heat and compression.
- the polymerizable layer Prior to reaction, has a lower viscosity when heated than the thermoplastic layer at the elevated temperatures. The compression and heat cause the lower viscosity polymerizable layer to flow faster than the thermoplastic resin layer.
- the multilayered laminate is preferably prepared as a five layer laminate comprised of a pair of outer layers of thermoplastic resin that sandwich two reinforcing fiber layers, which have a core of the polymerizable component layer.
- the polymerizable component layer permeates the reinforcing fiber layers, thereby coming into contact with the thermoplastic resin layer.
- the reactive compounds initially act as a flux and facilitate the penetration of thermoplastic resin into the reinforced fiber layers.
- the chemically reactive compounds come into the sphere of influence of the polymerization agent, which initiates/catalyzes the polymerization of the chemically reactive compounds.
- a portion of the chemically reactive compounds are carried to the surface of the multilayered laminate, wherein they continue to polymerize forming a Class-A surface, that is substantially fiber free.
- the thermoplastic resin thoroughly permeates the reinforcing fiber forming a composite having a core with a nearly uniform mixture of reinforced fiber and interstitial polymer, and a surface layer comprised of the now polymerized chemically reactive compounds.
- the finish of the surface coating substantially replicates the mold or compression plate.
- the thermoplastic layer can be compounded to include other additives such as reinforcing fibers, extenders which are fillers, antioxidants, UV stabilizers, thermal stabilizers, flame retardants, fillers which are reinforcing, glass beads, colorants, antimicrobial agents, dyes, pigments, plasticizers, oils, impact modifiers, processing aides (i.e. waxes, fluorinated compounds, silicone compounds, surfactants, polymeric processing aides), density modifiers such as phenolic beads, desiccants, buffers, and IR absorbent compounds to facilitate heating (i.e. carbon blacks, graphite, metal oxides).
- the polymerizable component layer and the reinforced fiber layer can contain similar additives.
- the principal object of the present invention is to provide an improved composition for forming a fiber reinforced thermoplastic composite, that following compression and heating, said composite has a Class-A surface.
- a further object of this invention is to provide an improved composition for forming a fiber reinforced composite, wherein the surface of the composite has a polymerized coating with attendant resistance to chemical etching.
- a further object of this invention is to provide a composition for a fiber reinforced laminate material, wherein the core of the composite is comprised of polymer that is integrally admixed with the reinforcing fibers.
- Another object of the invention is to provide an improved composition for a GMT composite, wherein parts fabricated from a GMT composite can either be in-mold coated or painted in subsequent steps for use in exterior body panel applications in automotive and transportation markets.
- FIG. 1 depicts the layered structure of the laminate sheet being consolidated using a double belt laminator.
- FIG. 2 shows the formation of the resin rich surface of the composite formed in the tool.
- the invention is a GMT laminate material that following thermoforming or compression molding forms a GMT laminate part with a Class-A surface, wherein the GMT part is suitable for applications as an exterior body panel.
- the body part can be either in-mold coated, or painted in subsequent steps for use in exterior body panel applications in the automotive and transportation markets.
- the GMT laminate material 10 is typically a five-layered structure consisting of two layers of reinforcing fibrous mat sandwiching a polymerizable component core layer and an overlayer of thermoplastic resin on either side of the reinforcing fibrous mat.
- the polymerizable component layer 14 and the two thermoplastic resin layers, 12 and 22 are extruded on the layers of glass fibrous mat, 16 and 18 , as shown in FIG. 1 .
- This five-layered structure is passed through a double belt laminator consisting of heated belts, 42 and 40 , to melt and impregnate the resin through the glass fibrous mat, therein consolidating the structure.
- a pair of cooling belts, 52 and 50 removes the heat and solidifies the resins to form a laminate 10 of the GMT material.
- the GMT laminate material 10 fuses forming a composite with a Class A surface 100 .
- the core 102 is comprised of the glass fibers integrally mixed with the thermoplastic resin.
- the surface of the composite 100 has a resin rich surface 104 substantially comprised of the chemically reactive component that is now polymerized. Note, under heat and pressure, the chemically reactive component has migrated from the core to the surface of the composite.
- a preferred thermoplastic resin comprising the thermoplastic resin layer is a polycarbonate resin that has melt flow index (MFI) greater than 5 and less than 28, with a preferred MFI greater than 12.
- the preferred polycarbonate is based on bisphenol-A.
- the polycarbonate resin is compounded with a filler, calcium carbonate, a reinforcing chopped fiber, and a polymerization agent.
- the preferred polymerization agent can be a free radical, anionic or transesterification catalyst.
- the polymerizable component is to be polymerized via transesterification.
- Suitable transesterification catalyst for polymerizing macrocyclic oligoesters are selected from the group consisting of organotin and organotitanate compounds.
- organotin compounds are dibutyltin dioxide, 1,1,6,6-tetra-n-butyl-1,6-distanna-2,5,7,10-tetraoxacyclodecane, n-butyltin(IV) chloride dihydroxide, dialkyltin(IV) oxides, such as di-n-butyltin(IV) oxide and di-n-octyltin oxide, and acyclic and cyclic monoalkyltin(IV) derivatives such as n-butyltin tri-n-butoxide, dialkyltin(IV) dialkoxides such as di-n-butyltin(IV) di-n-butoxide and 2,2-di-n-butyl-2-stanna-1,3-dioxacycloheptane, and trialkyltin alkoxides such as tributyltin ethoxide.
- dialkyltin(IV) oxides
- organotitanate compounds are tetra-isopropyl titanate tetra(2-ethylhexyl) titanate, tetraisopropyl titanate, and tetrabutyl titanate, and isopropyl triethanolaminatotitanate.
- These catalyst can also be employed when the polymerizable composition includes a monomer, such as a cyclic ester (i.e. ⁇ -caprolactone), which can be added to reduce the melting point of the macrocyclic polyester oligomers.
- the polymerizable component layer is preferably comprised of a macrocyclic oligoester).
- the polymerizable component layer is comprised of reactive compounds, preferably a macrocyclic polyester oligomers, also known as a macrocyclic oligoester.
- the macrocyclic oligoester contains 2 or more identifiable ester functional repeat units of the same or different formula.
- the macrocyclic oligoester typically refers to multiple molecules of one specific formula having varying ring sizes. However, a macrocyclic oligoester may also include multiple molecules of different formulae having varying numbers of the same or different structural repeat units.
- a macrocyclic oligoester may be a co-oligoester or multi-oligoester, i.e., an oligoester having two or more different structural repeat units having an ester functionality within one cyclic molecule.
- the macrocyclic oligoester preferably has 3-20 structural repeat units. Macrocyclic polyesters have very low viscosities compared to similar weight linear oligomers. In the presence of a polymerization agent, macrocyclic oligoesters can be rapidly polymerized, by ring opening, forming substantially linear polyesters having a much higher molecular weight. Typical molecular weights are in the range form about 90,000 to in excess of 150,000. The reaction has a relatively low exotherm.
- Preferred macrocyclic oligoesters are macrocyclic oligoesters of 1,4-butylene terephthalate (CBT), 1,3-propylene terephthalate (CPT), 1,4-cyclohexylenedimethylene terephthalate (CCT), ethylene terephthalate (CET), and 1,2-ethylene 2,6-naphthalenedicarboxylate (CEN).
- CBT 1,4-butylene terephthalate
- CPT 1,3-propylene terephthalate
- CCT 1,4-cyclohexylenedimethylene terephthalate
- CET ethylene terephthalate
- CEN 1,2-ethylene 2,6-naphthalenedicarboxylate
- the scope of the invention includes macrocyclic oligoesters of polyethylene isophthalate, sulfonated polyethylene isophthalate, sulfonated polyalkylene terephthalate, sulfonated polyalkylene naphthenate, and sulfonated polyalkylene isophthalate.
- monomers can be added, serving principally as diluents and also cross-linkers.
- Macrocyclic oligoesters can be blended to change the miscibility of the macrocyclic oligoester in the thermoplastic resin, and to change the melting point.
- linear oligomers can be admixed with macrocyclic oligoesters to lower the melting point.
- CBT resins are solid (powder, pellet, flake) at room temperature and when heated are fully molten above 150° C. (300° F.), with a viscosity in the range of 150 mPa ⁇ s (150 cP), and drops in viscosity to below 20 mPa ⁇ s (20 cP) at 180° C. (355° F.).
- the PBT macrocyclic oligoesters open and connect (i.e., polymerize) to form high molecular weight PBT thermoplastic without exotherm or off-gassing. Full polymerization can occur in 10's of seconds or many minutes depending on the temperature and type of catalyst used.
- the initial water-like viscosity enables the resin to migrate to the surface during B-stage processing.
- polycarbonate having a MFI of 18-24 has a viscosity 40,000 mPa (40,000 cP) at 600° F.
- CBT has a viscosity of 5 mPa (5 cP).
- the polymerizable component layer has a significant percentage of polycarbonate to improve the filmic properties, wherein the polycarbonate can make up to 80% of the extruded polymerizable component layer.
- Example 1 An example of the invention is given in Example 1.
- a 2.1 oz/sq. ft glass fiber mat is extrusion coated with a filled polycarbonate resin.
- MFI Melt Flow Index
- MFR Melt Flow Rate
- Dupont de Nemours under trade name Tyzor AA105 is a catalyst for the transesterification polymerization of macrocyclic oligoesters.
- the isopropyl triethanolaminatotitanate is compounded with the polycarbonate resin at 0.5 mol %.
- the thermoplastic resin is extruded at about 2 oz/sq. ft.
- a second glass fiber mat weighing 2.1 oz/sq. ft containing is similarly coated.
- Coextruded between the two mats is a polymerizable component layer comprised of about 75% by weight GE Lexan HF1110 polycarbonate and 25% by weight cyclic butylene tererpthalate macrocyclic oligoester (CBT) mixture.
- the polymerizable component layer extrudate weighs about 8 oz/sq. ft.
- the total weight of the five layer GMT structure is about 16 oz/sq. ft.
- the five layer structure is pressed in a heated press with platen surface temperature measuring 600° F. for about 4 minutes.
- the platens are held at a constant gap of 3 mm.
- the heated product is transported to a cooling press and cooled to room temperature under pressure at a constant gap of 3 mm for about 4 minutes, forming a GMT laminate material.
- the cooled laminate sheet is then trimmed, sheared and sectioned into 8′′ square panels.
- the laminate material is heated in an IR oven to 600° F. for 120 seconds and thermoformed or compression molded in a heated tool held at 200° F. with a pressure of 2 tons/sq in.
- the resulting composite has a uniform core of polycarbonate and GMT and a Class A surface with a tool surface finish.
- the composite has an impact strength and tensile as shown below.
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Abstract
A composition of a fiber reinforced laminate material that when thermoformed or compression molded forms a composite having a Class-A surface that is resin rich. The laminate material has a layer of a thermoplastic resin with an initiator and catalyst; a glass mat; an intra-layer of a polymerizable component that is a lower viscosity mixture of oligomers, monomers and thermoplastic resin; a second glass mat, and another layer of a thermoplastic resin with an initiator and catalyst. When thermoformed or compression molded, the combination of heat and pressure force the low viscosity polymerizable component through the permeable glass mats and toward the surface. The initiator and catalyst cause the polymerizable component to polymerize forming a Class-A surface that is resin rich. The thermoplastic resin thoroughly permeates the reinforcing fiber forming a composite having a core with a nearly uniform mixture of reinforced glass fiber and thermoplastic resin.
Description
- The present invention relates to a glass mat thermoplastic (GMT) composite, and more particularly to glass mat thermoplastic (GMT) composite having a Class-A surface made with a blend of thermoplastic resins and polymerizable moieties providing a resin rich surface finish when heated and molded using thermoforming and compression molding tools.
- There is a growing demand by industry, governmental regulatory agencies and consumers for durable and inexpensive products that are functional comparable or superior to metal products. This is particularly true in the automotive industry. Developers and manufacturers of these products are concerned with the strength parameters, such as impact, bending, stretching, and twisting resilience. To meet these demands, a number of composite materials have been engineered. A relatively inexpensive product is GMT composite. GMT composites can molded and stamped into a variety suitable products, most notably are bumpers. Previous known GMT products do not have sufficiently surface qualities to be used in visible applications on automobiles, such as body panels. The quality of the finish has to be suitable for painting, and this surface finish is designated a Class-A surface. Currently only sheet molded compounds (SMC) are used on visible, painted automobile body components. SMCs are substantially more expensive than GMT fabricated parts, and generate a lot of scrap. What is needed is a GMT that has a Class-A surface that can be used in visible, painted parts. A review of the prior art follows:
- Applicant is aware of the following U.S. patents.
U.S. Pat. No. Inventor Issue Date Title 4,983,247 Kim Jan. 8, 1991 METHOD FOR PRODUCING RESIN RICH SURFACE LAYER ON COMPOSITE THERMOPLASTIC MATERIAL 5,464,585 Fitzgibbon Nov. 7, 1995 METHOD OF INJECTION MOLDING ARTICLES WITH SELECTIVE CONCENTRATIONS OR GRADIENTS OF MATERIALS 4,612,238 Della Vecchia Sept 16, 1986 FIBER REINFORCED MULTI-PLY STAMPABLE THERMOPLASTIC SHEET - Kim, in U.S. Pat. No. 4,983,247, teaches a method for making a fiber reinforced composite having a resin rich first layer on the surface. Forming a fiber free layer of a thermoplastic resin, heating a composite bulk layer of resin and reinforcing fibers, and then compressing the first layer and the composite bulk layer, so that the heat from the bulk layer causes the first layer to melt.
- Fitzgibbon, in U.S. Pat. No. 5,464,585, teaches a method where a resin-modifying auxiliary material is concentrated in the surface portion of an article. The method is particularly suited to RIM (reaction injection molding). In the process the mold is filled with a gradient of a bulk material and an auxiliary material, where the auxiliary material is generally defined as producing superior results as a mold surface material. The ratio is varied with time, so that as the mold is filled there is less of the auxiliary material. Cited along with resin-modifying auxiliary materials are a catalyst and catalyst/initiator for polymerization, wherein they are concentrated at the surface of the mold.
- Della Vecchia et al, in U.S. Pat. No. 4,612,238, discloses a process for producing a laminate that combines a layer of resin, a glass mat, another layer of resin, a second glass mat, and a third layer of resin. The first and third layers of resin, which are thermoplastic materials, can be selected so as to obtain the desired properties. Various quantities of reinforcing materials, fillers and additives can be in selected proportions.
- The invention is a method for manufacturing and composition of a fiber reinforced laminate material of a multi-layered laminate having two or more layers, wherein following heating and compression molding or thermoforming the laminate material forms a composite having a Class-A surface that is resin rich. The fiber reinforced laminate material is typically utilized to make GMT composites that have a Class-A surface. The fiber reinforced laminate material is a multi-layered laminate that is formed with two or more layers, comprising: a layer comprised of a thermoplastic resin; a layer comprised of a polymerizable component comprised of chemically reactive components; and/or a layer of reinforcing fibers. The layers can be combined such that there is at least one layer of reinforcing fibers and a layer of a thermoplastic resin (A laminate), or at least one layer of reinforcing fibers and a layer of a polymerizable component (B laminate). The A laminate can in a subsequent coating, or simultaneously, be extrusion coated with a layer of the polymerizable component forming a three layer laminate (C laminate). Alternatively, the B laminate can in a subsequent coating, or simultaneously, be extrusion coated with a layer of the thermoplastic resin, which therein forms a three layer laminate that is also the C laminate. It obviously follows that the multi-layered laminates can be other combinations of the at least two layer laminate. For instance, CBBC and CCC, or two A laminates could be combined with an extrusion coating of the polymerizable component layer, wherein the thermoplastic resin layers are outer layers. This last combination is the conventional five layer GMT composite. Typically, the thermoplastic resin layer is further comprised of a polymerization agent selected from the group consisting of initiators, accelerators, cross-linkers, catalysts, drying agents, and a combination thereof. The polymerization agent need not be equally distributed throughout the thermoplastic resin, but can be added as a coating to the layer of thermoplastic resin. The polymerizable component layer and the thermoplastic resin layer are preferably separated by the layer of reinforcing fibers. The polymerizable component contains chemically reactive compounds selected from the group consisting of low molecular weight polymers, macrocyclic oligomers, oligomers, prepolymers, monomers, dimers, trimers, tetramers and the like, or any combination thereof. The polymerizable component can be further comprised of a thermoplastic polymer, such as the thermoplastic resin. The reinforced fiber layer is comprised of fibers selected from the group consisting of glass fibers, metal fibers, ceramic fibers, carbon fibers, aramid fibers, synthetic polymers made from polymers such as polyester, polypropylene, polyamides, polyimides, and polyurethanes, and blends of combinations thereof. The fibers can be chopped, matted, picked, bonded, woven, and other wised processed to optimize handling, saturation, cost, strength and orientation. In a preferred embodiment the thermoplastic layer is extruded onto a first side of the layer of reinforcing fibers, and the polymerizable component layer is extruded onto the opposing side of the reinforcing fiber layer. The chemically reactive compounds and the polymerization agents are selected so that when heated, the chemically reactive compounds polymerize forming a Class-A surface finish. The reinforcing fiber layer is selected so as to impart strength to the laminate following B-stage processing. In B-stage processing, at least one A laminate is combined with the polymerizable component or the C laminate in a thermoforming or compression molding process, wherein the laminates are heated and molded under compression. Preferably the laminates are combined such that the polymerizable component is sandwiched by the reinforcing fiber layers.
- The reinforcing fiber layer is further selected to be sufficiently open as to be permeable to impregnation/saturation by the thermoplastic resin, and to enable the permeation of the chemically reactive components, when the laminate is under heat and compression. Prior to reaction, the polymerizable layer has a lower viscosity when heated than the thermoplastic layer at the elevated temperatures. The compression and heat cause the lower viscosity polymerizable layer to flow faster than the thermoplastic resin layer.
- To produce the GMT composite having a Class-A surface, the multilayered laminate is preferably prepared as a five layer laminate comprised of a pair of outer layers of thermoplastic resin that sandwich two reinforcing fiber layers, which have a core of the polymerizable component layer. In B-stage processing, under heat and pressure the polymerizable component layer permeates the reinforcing fiber layers, thereby coming into contact with the thermoplastic resin layer. The reactive compounds initially act as a flux and facilitate the penetration of thermoplastic resin into the reinforced fiber layers. Similarly, the chemically reactive compounds come into the sphere of influence of the polymerization agent, which initiates/catalyzes the polymerization of the chemically reactive compounds. A portion of the chemically reactive compounds are carried to the surface of the multilayered laminate, wherein they continue to polymerize forming a Class-A surface, that is substantially fiber free. The thermoplastic resin thoroughly permeates the reinforcing fiber forming a composite having a core with a nearly uniform mixture of reinforced fiber and interstitial polymer, and a surface layer comprised of the now polymerized chemically reactive compounds. The finish of the surface coating substantially replicates the mold or compression plate.
- The thermoplastic layer can be compounded to include other additives such as reinforcing fibers, extenders which are fillers, antioxidants, UV stabilizers, thermal stabilizers, flame retardants, fillers which are reinforcing, glass beads, colorants, antimicrobial agents, dyes, pigments, plasticizers, oils, impact modifiers, processing aides (i.e. waxes, fluorinated compounds, silicone compounds, surfactants, polymeric processing aides), density modifiers such as phenolic beads, desiccants, buffers, and IR absorbent compounds to facilitate heating (i.e. carbon blacks, graphite, metal oxides). Similarly the polymerizable component layer and the reinforced fiber layer can contain similar additives.
- In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the detailed construction and to the arrangements of the components set forth in the following description illustrated in the drawings. The invention is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of the description and should not be regarded as limiting.
- The principal object of the present invention is to provide an improved composition for forming a fiber reinforced thermoplastic composite, that following compression and heating, said composite has a Class-A surface.
- A further object of this invention is to provide an improved composition for forming a fiber reinforced composite, wherein the surface of the composite has a polymerized coating with attendant resistance to chemical etching.
- A further object of this invention is to provide a composition for a fiber reinforced laminate material, wherein the core of the composite is comprised of polymer that is integrally admixed with the reinforcing fibers.
- Another object of the invention is to provide an improved composition for a GMT composite, wherein parts fabricated from a GMT composite can either be in-mold coated or painted in subsequent steps for use in exterior body panel applications in automotive and transportation markets.
- The foregoing and other objects will become more readily apparent by referring to the following detailed description and the appended drawings in which:
-
FIG. 1 depicts the layered structure of the laminate sheet being consolidated using a double belt laminator. -
FIG. 2 . shows the formation of the resin rich surface of the composite formed in the tool. - The invention is a GMT laminate material that following thermoforming or compression molding forms a GMT laminate part with a Class-A surface, wherein the GMT part is suitable for applications as an exterior body panel. The body part can be either in-mold coated, or painted in subsequent steps for use in exterior body panel applications in the automotive and transportation markets. The
GMT laminate material 10 is typically a five-layered structure consisting of two layers of reinforcing fibrous mat sandwiching a polymerizable component core layer and an overlayer of thermoplastic resin on either side of the reinforcing fibrous mat. Thepolymerizable component layer 14 and the two thermoplastic resin layers, 12 and 22, are extruded on the layers of glass fibrous mat, 16 and 18, as shown inFIG. 1 . This five-layered structure is passed through a double belt laminator consisting of heated belts, 42 and 40, to melt and impregnate the resin through the glass fibrous mat, therein consolidating the structure. A pair of cooling belts, 52 and 50, removes the heat and solidifies the resins to form alaminate 10 of the GMT material. As shown inFIG. 2 , under heat and pressure theGMT laminate material 10 fuses forming a composite with aClass A surface 100. Thecore 102 is comprised of the glass fibers integrally mixed with the thermoplastic resin. The surface of the composite 100 has a resinrich surface 104 substantially comprised of the chemically reactive component that is now polymerized. Note, under heat and pressure, the chemically reactive component has migrated from the core to the surface of the composite. - A preferred thermoplastic resin comprising the thermoplastic resin layer is a polycarbonate resin that has melt flow index (MFI) greater than 5 and less than 28, with a preferred MFI greater than 12. The preferred polycarbonate is based on bisphenol-A. The polycarbonate resin is compounded with a filler, calcium carbonate, a reinforcing chopped fiber, and a polymerization agent. The preferred polymerization agent can be a free radical, anionic or transesterification catalyst. In the instant case, the polymerizable component is to be polymerized via transesterification. Suitable transesterification catalyst for polymerizing macrocyclic oligoesters, are selected from the group consisting of organotin and organotitanate compounds. Examples of organotin compounds are dibutyltin dioxide, 1,1,6,6-tetra-n-butyl-1,6-distanna-2,5,7,10-tetraoxacyclodecane, n-butyltin(IV) chloride dihydroxide, dialkyltin(IV) oxides, such as di-n-butyltin(IV) oxide and di-n-octyltin oxide, and acyclic and cyclic monoalkyltin(IV) derivatives such as n-butyltin tri-n-butoxide, dialkyltin(IV) dialkoxides such as di-n-butyltin(IV) di-n-butoxide and 2,2-di-n-butyl-2-stanna-1,3-dioxacycloheptane, and trialkyltin alkoxides such as tributyltin ethoxide. Examples of organotitanate compounds are tetra-isopropyl titanate tetra(2-ethylhexyl) titanate, tetraisopropyl titanate, and tetrabutyl titanate, and isopropyl triethanolaminatotitanate. These catalyst can also be employed when the polymerizable composition includes a monomer, such as a cyclic ester (i.e. ε-caprolactone), which can be added to reduce the melting point of the macrocyclic polyester oligomers. The polymerizable component layer is preferably comprised of a macrocyclic oligoester). The polymerizable component layer is comprised of reactive compounds, preferably a macrocyclic polyester oligomers, also known as a macrocyclic oligoester. The macrocyclic oligoester contains 2 or more identifiable ester functional repeat units of the same or different formula. The macrocyclic oligoester typically refers to multiple molecules of one specific formula having varying ring sizes. However, a macrocyclic oligoester may also include multiple molecules of different formulae having varying numbers of the same or different structural repeat units. A macrocyclic oligoester may be a co-oligoester or multi-oligoester, i.e., an oligoester having two or more different structural repeat units having an ester functionality within one cyclic molecule. The macrocyclic oligoester preferably has 3-20 structural repeat units. Macrocyclic polyesters have very low viscosities compared to similar weight linear oligomers. In the presence of a polymerization agent, macrocyclic oligoesters can be rapidly polymerized, by ring opening, forming substantially linear polyesters having a much higher molecular weight. Typical molecular weights are in the range form about 90,000 to in excess of 150,000. The reaction has a relatively low exotherm. Preferred macrocyclic oligoesters are macrocyclic oligoesters of 1,4-butylene terephthalate (CBT), 1,3-propylene terephthalate (CPT), 1,4-cyclohexylenedimethylene terephthalate (CCT), ethylene terephthalate (CET), and 1,2-ethylene 2,6-naphthalenedicarboxylate (CEN). Macrocyclic multi-oligoesters are comprised of two or more of the above structural repeat units. The scope of the invention includes macrocyclic oligoesters of polyethylene isophthalate, sulfonated polyethylene isophthalate, sulfonated polyalkylene terephthalate, sulfonated polyalkylene naphthenate, and sulfonated polyalkylene isophthalate. As previously mentioned monomers can be added, serving principally as diluents and also cross-linkers. Macrocyclic oligoesters can be blended to change the miscibility of the macrocyclic oligoester in the thermoplastic resin, and to change the melting point. Also, linear oligomers can be admixed with macrocyclic oligoesters to lower the melting point. The mixing of isophthlate esters to terephthalate esters significantly reduces the crystallinity of the polymerized material. The main advantage of macrocyclic oligoesters over their linear counterpart is that upon melting they have a very low viscosity. For instance, CBT resins are solid (powder, pellet, flake) at room temperature and when heated are fully molten above 150° C. (300° F.), with a viscosity in the range of 150 mPa·s (150 cP), and drops in viscosity to below 20 mPa·s (20 cP) at 180° C. (355° F.). When mixed with specific tin or titanium polymerization catalysts the PBT macrocyclic oligoesters open and connect (i.e., polymerize) to form high molecular weight PBT thermoplastic without exotherm or off-gassing. Full polymerization can occur in 10's of seconds or many minutes depending on the temperature and type of catalyst used. The initial water-like viscosity enables the resin to migrate to the surface during B-stage processing. As a comparison of viscosity, polycarbonate having a MFI of 18-24 has a viscosity 40,000 mPa (40,000 cP) at 600° F., while CBT has a viscosity of 5 mPa (5 cP). Typically, the polymerizable component layer has a significant percentage of polycarbonate to improve the filmic properties, wherein the polycarbonate can make up to 80% of the extruded polymerizable component layer.
- An example of the invention is given in Example 1.
- A 2.1 oz/sq. ft glass fiber mat is extrusion coated with a filled polycarbonate resin. The polycarbonate resin is a GE Lexang HF1110 polycarbonate resin having a Melt Flow Index (MFI) listed as 18-24 g/10 min (a.k.a. Melt Flow Rate (MFR)=18-24 g/10 min). The polycarbonate resin is admixed with polymerization agent that is a titanate ester, isopropyl triethanolaminatotitanate. Isopropyl triethanolaminatotitanate is sold by E.I. Dupont de Nemours under trade name Tyzor AA105, and is a catalyst for the transesterification polymerization of macrocyclic oligoesters. The isopropyl triethanolaminatotitanate is compounded with the polycarbonate resin at 0.5 mol %. The thermoplastic resin is extruded at about 2 oz/sq. ft. A second glass fiber mat weighing 2.1 oz/sq. ft containing is similarly coated. Coextruded between the two mats is a polymerizable component layer comprised of about 75% by weight GE Lexan HF1110 polycarbonate and 25% by weight cyclic butylene tererpthalate macrocyclic oligoester (CBT) mixture. The polymerizable component layer extrudate weighs about 8 oz/sq. ft. The total weight of the five layer GMT structure is about 16 oz/sq. ft.
- The five layer structure is pressed in a heated press with platen surface temperature measuring 600° F. for about 4 minutes. The platens are held at a constant gap of 3 mm. The heated product is transported to a cooling press and cooled to room temperature under pressure at a constant gap of 3 mm for about 4 minutes, forming a GMT laminate material. The cooled laminate sheet is then trimmed, sheared and sectioned into 8″ square panels.
- In B-stage processing, the laminate material is heated in an IR oven to 600° F. for 120 seconds and thermoformed or compression molded in a heated tool held at 200° F. with a pressure of 2 tons/sq in. The resulting composite has a uniform core of polycarbonate and GMT and a Class A surface with a tool surface finish. The composite has an impact strength and tensile as shown below.
GLASS CONTENT % 29 IMPACT STRENGTH ft-lb./in. 20 TENSILE STRENGTH ksi 19.2 TENSILE MODULUS ksi 1045 MULTIAXIAL IMPACT ft-lbs 13.5 Max Load ft-lbs 20.3 Failure - From the foregoing, it is readily apparent that I have invented an improved composition for forming a fiber reinforced composite, wherein the surface of the composite has a resin coating that is substantially free of glass fibers. It is also apparent that I have provided a composition for a fiber reinforced laminate material, wherein, after thermoforming or molding, the core of the composite is substantially comprised of thermoplastic resin polymer that is integrally admixed with the reinforcing fibers. It is further apparent that the GMT laminate material, when processed by thermoforming or compression molding the resulting manufactured parts are suitable for use in exterior body panel applications in automotive and transportation markets.
- It is to be understood that the foregoing description and specific embodiments are merely illustrative of the best mode of the invention and the principles thereof, and that various modifications and additions may be made to the apparatus by those skilled in the art, without departing from the spirit and scope of this invention, which is therefore understood to be limited only by the scope of the appended claims.
Claims (42)
1. A composition of a fiber reinforced laminate material of a multi-layered laminate having two or more layers, wherein following heating using a compression molding or thermoforming process the laminate material forms a composite having a Class-A surface that is resin rich, said laminate material comprising:
a) a layer comprised of a thermoplastic resin;
b) a layer comprised of a polymerizable component comprised of chemically reactive components;
c) a layer of reinforcing fibers.
wherein the layer of reinforcing fibers is sufficiently open as to be permeable to impregnation/saturation by the thermoplastic resin and to enable the migration of the chemically reactive components, when the laminate is under heat and compression; and
wherein at the temperatures of molding the polymerizable component has a lower viscosity than the thermoplastic.
2. A composition of a fiber reinforced laminate material according to claim 1 , wherein the layer of thermoplastic resin further comprises a polymerization agent.
3. The composition of a fiber reinforced laminate material, as claimed in claim 2 , wherein the polymerization agent is selected from the group consisting of initiators, accelerators, cross-linkers, catalysts, drying agents or a combination thereof.
4. The composition of a fiber reinforced laminate material, as claimed in claim 1 , wherein the chemically reactive components are selected from the group consisting of low molecular weight polymers, macrocyclic oligomers, linear oligomers, prepolymers, monomers, cyclic esters, dimers, trimers, tetramers and the like, or any combination thereof.
5. A composition of a fiber reinforced laminate material, according to claim 1 , wherein the layer of chemically reactive components is further comprised of a thermoplastic polymer.
6. The composition of a fiber reinforced laminate material, as claimed in claim 5 , wherein the chemically reactive components are selected from the group consisting of low molecular weight polymers, oligomers, prepolymers, monomers, dimers, trimers, tetramers and the like, and any combination thereof.
7. The composition of a fiber reinforced laminate material, as claimed in claim 1 , wherein the reinforced fiber layer is comprised of fibers selected from the group consisting of glass fibers, metal fibers, ceramic fibers, carbon fibers, aramid fibers, synthetic polymers made from polymers such as polyester, polypropylene, polyamides, polyimides, and polyurethanes, and blends and combinations thereof.
8. The composition of a fiber reinforced laminate material, as claimed in claim 7 , wherein the reinforced fiber layer is comprised of fibers that are long, short, chopped, matted, picked, bonded, woven, and other wised processed to facilitate handling, saturation, cost, strength and orientation.
9. The composition of a fiber reinforced laminate material, as claimed in claim 1 , wherein the reinforced fiber layer is a glass mat.
10. The composition of a fiber reinforced laminate material, as claimed in claim 1 , wherein the thermoplastic resin is selected from the group consisting of polyolefins; polyesters, polyurethanes, polyacrylates, copolymers, terpolymers ionomers of copolymers.
11. The composition of a fiber reinforced laminate material, as claimed in claim 10 , wherein the thermoplastic polyolefin resin is selected from the group consisting of polypropylenes, ethylene propylene copolymers, ethylene propylene diene monomer, TPCs and TPEs.
12. A composition of a fiber reinforced laminate material according to claim 1 , wherein the layer of thermoplastic resin further comprises other additives selected from the group consisting of reinforcing fibers, extenders which are fillers, antioxidants, UV stabilizers, thermal stabilizers, flame retardants, fillers which are reinforcing, glass beads, colorants, antimicrobial agents, dyes, pigments, plasticizers, oils, impact modifiers, processing aides (i.e. waxes, fluorinated compounds, silicone compounds, surfactants, polymeric processing aides), density modifiers such as phenolic beads, desiccants, buffers, and IR absorbent compounds to facilitate heating (i.e. carbon blacks, graphite, metal oxides).
13. A composition of a fiber reinforced laminate material according to claim 1 , wherein the layer of polymerizable components further comprises other additives selected from the group consisting of reinforcing fibers, extenders which are fillers, antioxidants, UV stabilizers, thermal stabilizers, flame retardants, fillers which are reinforcing, glass beads, colorants, antimicrobial agents, dyes, pigments, plasticizers, oils, impact modifiers, processing aides (i.e. waxes, fluorinated compounds, silicone compounds, surfactants, polymeric processing aides), density modifiers such as phenolic beads, desiccants, buffers, and IR absorbent compounds to facilitate heating (i.e. carbon blacks, graphite, metal oxides).
14. A composition of a fiber reinforced laminate material according to claim 1 , wherein the layer of reinforcing fibers comprises other additives selected from the group consisting of extenders which are fillers, antioxidants, UV stabilizers, thermal stabilizers, flame retardants, fillers which are reinforcing, glass beads, colorants, antimicrobial agents, dyes, pigments, plasticizers, oils, impact modifiers, density modifiers such as phenolic beads, desiccants, buffers, and IR absorbent compounds to facilitate heating (i.e. carbon blacks, graphite, metal oxides).
15. A method for forming a fiber reinforced laminate material of a multi-layered laminate having three or more layers, wherein following heated compression molding, said composite has a Class-A surface that is resin rich, said method comprising the steps of:
a) extruding an intra-layer of polymerizable components between a first layer of reinforcing fibers and a second layer of reinforcing fibers;
b) essentially simultaneously extruding an first layer of thermoplastic resin on an outer side of the first layer of reinforcing fibers and a second layer of thermoplastic resin on an outer side of the second layer of reinforcing fibers; and,
c) laminating the first layer of thermoplastic resin, the first layer of reinforcing fibers, the intra-layer of polymerizable components, the second layer of reinforcing fibers and the second layer of thermoplastic resin; and
d) cooling the laminate, therein forming the fiber reinforced laminate material.
16. A method for forming a fiber reinforced laminate material according to claim 15 , wherein the layer of thermoplastic resin further comprises a polymerization agent.
17. The method for forming a fiber reinforced laminate material as claimed in claim 15 , wherein the wherein the polymerization agent is selected from the group consisting of initiators, accelerators, cross-linkers, catalysts, drying agents or a combination thereof.
18. The method for forming a fiber reinforced laminate material as claimed in claim 15 , wherein the layer of polymerizable components is comprised of chemically reactive components selected from the group consisting of low molecular weight polymers, oligomers, prepolymers, monomers, dimers, trimers, tetramers and the like, and any combination thereof.
19. The method for forming a fiber reinforced laminate material as claimed in claim 18 , wherein the polymerizable component is further comprised of a thermoplastic polymer.
20. The method for forming a fiber reinforced laminate material as claimed in claim 15 , wherein the first layer of reinforcing fiber is a glass mat, and the second layer of reinforcing fiber is also a glass mat, wherein the glass mat is selected for its appropriate application in a GMT composite.
21. The method for forming a fiber reinforced laminate material as claimed in claim 15 , wherein the thermoplastic resin selected from the group consisting of polyolefins, polyesters, polyurethanes, polyacrylates, copolymers, terpolymers ionomers of copolymers.
22. The method for forming a fiber reinforced laminate material as claimed in claim 21 , wherein the polyester resin is selected from the group consisting of polycarbonate, polyethylene terephthalate, polybutylene terephthalate or blends thereof.
23. The method for forming a fiber reinforced laminate material according to claim 15 , wherein the layer of thermoplastic resin further comprises other additives selected from the group consisting of reinforcing fibers, extenders which are fillers, antioxidants, UV stabilizers, thermal stabilizers, flame retardants, fillers which are reinforcing, glass beads, colorants, antimicrobial agents, dyes, pigments, plasticizers, oils, impact modifiers, processing aides (i.e. waxes, fluorinated compounds, silicone compounds, surfactants, polymeric processing aides), density modifiers such as phenolic beads, desiccants, buffers, and IR absorbent compounds to facilitate heating (i.e. carbon blacks, graphite, metal oxides).
24. The method for forming a fiber reinforced laminate material according to claim 15 , wherein the layer of polymerizable components comprises other additives selected from the group consisting of reinforcing fibers, extenders which are fillers, antioxidants, UV stabilizers, thermal stabilizers, flame retardants, fillers which are reinforcing, glass beads, colorants, antimicrobial agents, dyes, pigments, plasticizers, oils, impact modifiers, processing aides (i.e. waxes, fluorinated compounds, silicone compounds, surfactants, polymeric processing aides), density modifiers such as phenolic beads, desiccants, buffers, and IR absorbent compounds to facilitate heating (i.e. carbon blacks, graphite, metal oxides).
25. The method for forming a fiber reinforced laminate material according to claim 15 , wherein the layer of reinforcing fibers comprises other additives selected from the group consisting of extenders which are fillers, antioxidants, UV stabilizers, thermal stabilizers, flame retardants, fillers which are reinforcing, glass beads, colorants, antimicrobial agents, dyes, pigments, plasticizers, oils, impact modifiers, density modifiers such as phenolic beads, desiccants, buffers, and IR absorbent compounds to facilitate heating (i.e. carbon blacks, graphite, metal oxides).
26. The composition of a fiber reinforced laminate material, as claimed in claim 10 , wherein the polyester resin is selected from the group consisting of polycarbonate, polyethylene terephthalate, polybutylene terephthalate or blends thereof.
27. The composition of a fiber reinforced laminate material as claimed in claim 1 , wherein on exposure to heat and pressure a portion of the chemically reactive components are forced to the surface of the fiber reinforced laminate material, therein the reactive components polymerize forming a Class-A surface, that is substantially fiber free.
28. The method for forming a fiber reinforced laminate material according to claim 15 , wherein on exposure to heat and pressure a portion of the chemically reactive components are forced to the surface of the fiber reinforced laminate material, therein the reactive components polymerize forming a Class-A surface that is substantially fiber free, and wherein the thermoplastic resin thoroughly permeates the reinforcing fiber forming a composite having a core with a nearly uniform mixture of reinforced fiber and thermoplastic resin.
29. The composition of a fiber reinforced laminate material, as claimed in claim 2 , wherein the thermoplastic resin is polycarbonate.
30. The composition of a fiber reinforced laminate material, as claimed in claim 2 , wherein the polymerization agent is a transesterification catalyst.
31. The composition of a fiber reinforced laminate material, as claimed in claim 30 , wherein the transesterification catalyst is a titanate ester.
32. The composition of a fiber reinforced laminate material, as claimed in claim 31 , wherein the titanate ester is isopropyl triethanolaminatotitanate.
33. The composition of a fiber reinforced laminate material, as claimed in claim 4 , wherein the macrocyclic oligomers is a macrocyclic oligoester.
34. The composition of a fiber reinforced laminate material, as claimed in claim 33 , wherein the macrocyclic oligoester is selected from the group consisting of 1,4-butylene terephthalate (CBT), 1,3-propylene terephthalate (CPT), 1,4-cyclohexylenedimethylene terephthalate (CCT), ethylene terephthalate (CET), 1,2-ethylene 2,6-naphthalenedicarboxylate (CEN), macrocyclic oligoesters of polyethylene isophthalate, sulfonated polyethylene isophthalate, sulfonated polyalkylene terephthalate, sulfonated polyalkylene naphthenate, and sulfonated polyalkylene isophthalate.
35. The composition of a fiber reinforced laminate material, as claimed in claim 34 , wherein the preferred macrocyclic oligoester is 1,4-butylene terephthalate (CBT).
36. The composition of a fiber reinforced laminate material, as claimed in claim 1 , wherein one of the chemically reactive components is a thermoplastic resin is polycarbonate.
37. The composition of a fiber reinforced laminate material, as claimed in claim 36 , wherein the polycarbonate comprises greater 50% of the weight of the polymerizable component layer.
38. The composition of a fiber reinforced laminate material, as claimed in claim 2 , wherein the thermoplastic resin has a MFI greater than 5.
39. The composition of a fiber reinforced laminate material, as claimed in claim 34 , wherein the macrocyclic oligoester has a repeating structural unit of 3-20 units.
40. The composition of a fiber reinforced laminate material, as claimed in claim 30 , wherein the transesterification catalyst is admixed with the thermoplastic resin.
41. The composition of a fiber reinforced laminate material, as claimed in claim 40 , wherein the weight percentage of transesterification catalyst in the layer of thermoplastic resin is less than 1%.
42. The composition of a fiber reinforced laminate material, as claimed in claim 40 , wherein the weight percentage of glass fiber of the weight of the composite material is 15% to 35%.
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EP04796167A EP1680273A2 (en) | 2003-10-30 | 2004-10-22 | Improved glass mat thermoplastic composite |
CNA200480032271XA CN1960858A (en) | 2003-10-30 | 2004-10-22 | Improved glass fiber felt thermoplastic composite |
JP2006538127A JP2007509783A (en) | 2003-10-30 | 2004-10-22 | Improved glass mat thermoplastic composite |
KR1020067008467A KR20060116199A (en) | 2003-10-30 | 2004-10-22 | Improved glass mat thermoplastic composite |
PCT/US2004/035119 WO2005044531A2 (en) | 2003-10-30 | 2004-10-22 | Improved glass mat thermoplastic composite |
US11/141,238 US7972685B2 (en) | 2003-10-30 | 2005-05-31 | Glass mat laminate comprised of polymerizable cyclic polyester oligomers suitable for composites with a class-A surface |
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3639424A (en) * | 1970-02-19 | 1972-02-01 | Eastman Kodak Co | Extrudable and moldable plastic compositions reinforced with heat set polyester fibers |
US4379802A (en) * | 1982-04-21 | 1983-04-12 | Eastman Kodak Company | Stampable reinforced thermoplastic polyester sheet with improved surface finish |
US4379801A (en) * | 1982-04-21 | 1983-04-12 | Eastman Kodak Company | Stampable reinforced thermoplastic polyester sheets |
US4612238A (en) * | 1977-07-18 | 1986-09-16 | Allied Corporation | Fiber reinforced multi-ply stampable thermoplastic sheet |
US4983247A (en) * | 1989-08-07 | 1991-01-08 | General Electric Company | Method for producing resin rich surface layer on composite thermoplastic material |
US5165990A (en) * | 1989-11-28 | 1992-11-24 | Idemitsu Kosan Co., Ltd. | Stampable sheet |
US5175198A (en) * | 1991-08-30 | 1992-12-29 | General Electric Company | Thermoformable/polycarbonate/woven glass cloth composites |
US5464585A (en) * | 1994-01-03 | 1995-11-07 | Metton America, Inc. | Method of injection molding articles with selective concentrations or gradients of materials |
US6369157B1 (en) * | 2000-01-21 | 2002-04-09 | Cyclics Corporation | Blend material including macrocyclic polyester oligomers and processes for polymerizing the same |
US6420047B2 (en) * | 2000-01-21 | 2002-07-16 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
US20050032452A1 (en) * | 2003-08-07 | 2005-02-10 | Helwig Gregory S. | Conformable surfacing veil or reinforcement mat |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0330960A3 (en) * | 1988-03-04 | 1990-07-11 | General Electric Company | Method of forming a fiber-reinforced thermoplastic article |
JPH0416314A (en) * | 1990-05-10 | 1992-01-21 | Mitsubishi Petrochem Co Ltd | Manufacture of fiber reinforced thermoplastic resin formed body |
JPH0767705B2 (en) * | 1992-01-29 | 1995-07-26 | ゼネラル・エレクトリック・カンパニイ | Method for improving surface shape of composite structure |
EP0589640A1 (en) * | 1992-09-24 | 1994-03-30 | General Electric Company | Macrocyclic molding compositions |
EP0640466A1 (en) * | 1993-08-11 | 1995-03-01 | General Electric Company | Process for compression moulding of a melt impregnated multilayer article |
US5482667A (en) * | 1993-08-11 | 1996-01-09 | General Electric Company | Extrusion impregnation compression molding process |
JPH07214729A (en) * | 1994-02-08 | 1995-08-15 | Mitsubishi Chem Corp | Fiber reinforced resin molded object and production thereof |
US5498651A (en) * | 1995-06-19 | 1996-03-12 | General Electric Company | Method for polymerizing macrocyclic polyester oligomers |
JP2721820B2 (en) * | 1995-08-10 | 1998-03-04 | 筒中プラスチック工業株式会社 | Fiber reinforced thermoplastic resin laminate |
JP3083257B2 (en) * | 1996-03-25 | 2000-09-04 | 池田物産株式会社 | Manufacturing method of interior materials |
JP2000062072A (en) * | 1998-08-18 | 2000-02-29 | Sekisui Chem Co Ltd | Manufacture of fiber reinforced thermoplastic resin sheet |
JP4219899B2 (en) * | 2001-05-14 | 2009-02-04 | 株式会社カネカ | Thermoplastic resin composition |
-
2003
- 2003-10-30 US US10/696,869 patent/US20050095415A1/en not_active Abandoned
-
2004
- 2004-10-22 KR KR1020067008467A patent/KR20060116199A/en not_active Application Discontinuation
- 2004-10-22 CN CNA200480032271XA patent/CN1960858A/en active Pending
- 2004-10-22 EP EP04796167A patent/EP1680273A2/en not_active Withdrawn
- 2004-10-22 JP JP2006538127A patent/JP2007509783A/en active Pending
- 2004-10-22 WO PCT/US2004/035119 patent/WO2005044531A2/en active Application Filing
-
2005
- 2005-05-31 US US11/141,238 patent/US7972685B2/en active Active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3639424A (en) * | 1970-02-19 | 1972-02-01 | Eastman Kodak Co | Extrudable and moldable plastic compositions reinforced with heat set polyester fibers |
US4612238A (en) * | 1977-07-18 | 1986-09-16 | Allied Corporation | Fiber reinforced multi-ply stampable thermoplastic sheet |
US4379802A (en) * | 1982-04-21 | 1983-04-12 | Eastman Kodak Company | Stampable reinforced thermoplastic polyester sheet with improved surface finish |
US4379801A (en) * | 1982-04-21 | 1983-04-12 | Eastman Kodak Company | Stampable reinforced thermoplastic polyester sheets |
US4983247A (en) * | 1989-08-07 | 1991-01-08 | General Electric Company | Method for producing resin rich surface layer on composite thermoplastic material |
US5165990A (en) * | 1989-11-28 | 1992-11-24 | Idemitsu Kosan Co., Ltd. | Stampable sheet |
US5175198A (en) * | 1991-08-30 | 1992-12-29 | General Electric Company | Thermoformable/polycarbonate/woven glass cloth composites |
US5464585A (en) * | 1994-01-03 | 1995-11-07 | Metton America, Inc. | Method of injection molding articles with selective concentrations or gradients of materials |
US6369157B1 (en) * | 2000-01-21 | 2002-04-09 | Cyclics Corporation | Blend material including macrocyclic polyester oligomers and processes for polymerizing the same |
US6420047B2 (en) * | 2000-01-21 | 2002-07-16 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
US6639009B2 (en) * | 2000-01-21 | 2003-10-28 | Cyclis Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
US6994914B2 (en) * | 2000-01-21 | 2006-02-07 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
US20050032452A1 (en) * | 2003-08-07 | 2005-02-10 | Helwig Gregory S. | Conformable surfacing veil or reinforcement mat |
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Also Published As
Publication number | Publication date |
---|---|
US20050228108A1 (en) | 2005-10-13 |
CN1960858A (en) | 2007-05-09 |
JP2007509783A (en) | 2007-04-19 |
WO2005044531A3 (en) | 2006-05-18 |
KR20060116199A (en) | 2006-11-14 |
EP1680273A2 (en) | 2006-07-19 |
US7972685B2 (en) | 2011-07-05 |
WO2005044531A2 (en) | 2005-05-19 |
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