CN101600568A - Rigid pvc melt bonded thermoplastic elastomer composite material - Google Patents
Rigid pvc melt bonded thermoplastic elastomer composite material Download PDFInfo
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- CN101600568A CN101600568A CNA2008800037278A CN200880003727A CN101600568A CN 101600568 A CN101600568 A CN 101600568A CN A2008800037278 A CNA2008800037278 A CN A2008800037278A CN 200880003727 A CN200880003727 A CN 200880003727A CN 101600568 A CN101600568 A CN 101600568A
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Abstract
The bonding composition for thermoplastic elastomer of hard PVC melting is disclosed.The melt bonded composite of being made by these compositions has with thermoplastic elastomer or the rigid vinyl chloride polymer layer extruded with the foamed thermoplastic elastomer layer.This composite can be used as the backing and the sealant of PVC plate, PVC plate; Vinyl floor, door and window; PVC conveyer belt external grid layer; Door and window slip strip of paper used for sealing; The door and window mine dam; Seal with pvc pipe.
Description
Background of invention
Hard PVC-cohesible thermoplastic elastomer (TPE) is disclosed.Said composition provides melt bonded thermoplastic elastomer to the RPVC layer.This composite can be used for the sealing and various building occupancy, and they can extensively be used in extrude with injection moulding in.
Summary of the invention
Vinyl chloride-base polymer (PVC) is because they have concurrently low-cost and availability and extensively being used in the outdoor architecture purposes.But the restriction of PVC comprises the weatherability of fragility, difference, the durability and the low-yield efficient of difference.Can use rubber impact modifiers and sealant to improve the character of PVC.But, be difficult to substrate with timber, metal or plastics and so on and be adhered to that PVC goes up and few resin has the compatibility melt bonded with PVC.Therefore, apply adhesive so that formation is bonding between PVC and other resin and rubber, thereby form laminate.But this method is labor-intensive and may causes lamination inferior.
US 4,680, and 234 have described a kind of flexible weather-proof film, its comprise vinyl chloride-base polymer and haloflex blend weathering layer and contain the second layer that is generally solid-state thermoplastic adhesives.When ground floor comprises ethene and at least a interpretation that contains the undersaturated carboxylic acid of ethylenic or its ester in addition, obtain improved performance.
US 5,143,772 have described the rubber-moulding goods with ornamenting layer, it comprises the rubber-moulding goods main body made by EPDM, at PVC composition ornamenting layer that forms on this main body and the adhesive layer that between this main body and this ornamenting layer, forms, described adhesive layer comprises the EPDM of NBR, 20 to 40 weight % of 40 to 80 weight % and the SBR of 0 to 35 weight %; The method of making described rubber-moulding goods has also been described.The rubber-moulding goods of this invention provide the inside and outside automobile decoration with improved decoration design with high production rate.
US 5,302, and 650 have described a kind of vinyl chloride resin composition, and it comprises: the mixture that is made of 10 to 97 weight % vinyl chloride resins and 3 to 90 weight % thermoplastic polyester elastomers; With the described mixture with respect to 100 weight portions, the plasticizer of 10 to 200 weight portions, the molecular weight of described plasticizer are 500 to 5000.This vinyl chloride resin composition can be easily melt bonded to being not easy traditionally on the melt bonded polycarbonate resin.Therefore, said composition can extensively be used in extrusion molding and the injection moulding.In addition, owing to use high molecular weight plasticizer, can overcome crack problem as plasticizer.In addition, owing in this autofrettage, needn't use adhesive, can significantly reduce totle drilling cost.
US 5,334,450 have described and have been used to be laminated to non-weather-proof suprabasil Weather-proof film, comprise for example three-layer thin-film structure, comprise: the first surface layer that at least one is made of weather-proof polymer, described weather-proof polymer comprises (a) AES, ASA, SAN or its mixture or (b) and any polymer of (a) of PVC, CPE, aliphatic urethane or saturated styrene block copolymer blend, described layer has greater than 150 1% secant modulus of 000psi; At least one second intermediate layer, it is the tack coat below this weathering layer, and described intermediate adhesive layer is adjoined and is pasted on this weathering layer, and described intermediate adhesive layer has less than 150, the modulus of 000psi; Described tack coat could be adhered on the three below layer at least; With at least one the 3rd layer below this tack coat, described the 3rd layer is adjoined and pastes on the tack coat, and described the 3rd layer has less than 150 the modulus of 000psi.
US 5,380, and 797 have described the high impact polymer blend that contains at least two kinds of two-phase or multiphase polymer Ps 1 and P2, and described two-phase or multiphase polymer contains at least one toughness reinforcing phase A1 or A2 and at least one hard B1 or B2 mutually again.Different and the thermodynamic compatibility each other of the chemical constitution of B1 and B2.Optional another thermoplastic polymer B ' 3 and/or another two-phase or multiphase polymer P 4 of containing of this polymer blend, described two-phase or multiphase polymer contains at least one toughness reinforcing phase A4 and at least one hard B4 mutually, condition be B ' 3 and/or B4 be different from B1 and B2 and with B1 and B2 thermodynamic compatibility.
US 5,403, and 892 have described a kind of thermoplastic compounds of dynamic vulcanization, and it comprises the polymer blend of following ingredients: (a) thermoplastic olefin resin, as the inelastic body EVAc; (b) has the elastomeric ethylene vinyl acetate copolymer of relative higher vinyl acetate content; (c) elastomer copolymer of appointment is as halobutyl rubber, EPDM or C
4To C
7Isomonoolefin with to the halogenated copolymers of ring-alkylated styrenes.Also can in said composition, mix halogenated polyethylene.The thermoplastic compounds of this dynamic vulcanization is fit to be adhered on the polyvinyl chloride.
US 5,415, and 921 have described the laminate that can be used as construction material.This laminate has the basalis that contains vinyl chloride-base polymer, butadiene rubber graft copolymer, and has the overlying strata that contains vinyl chloride-base polymer, butyl acrylate rubber graft copolymer and titanium dioxide.This overlying strata prevents the basalis over-exposure in ultraviolet ray, heat and down wet, and prevents the basalis weathering in this laminate as the outdoor application process that is used for the material of wallboard, channel system, downpipe, blind window, window frame and other outdoor weathering construction material purposes thus.
US 6,195, and 952 have described compound fastening vinyl plate or other glued board, and it has with permanent flexible adhesive (itself and vinyl and insulating materials is all compatible and can not harden) and is adhered to the elongated insulation component on the vinyl plate.The front that this insulation component is configured to make this insulating materials accurately with the contour convergence in ethene element front.This insulation component forms the ramus superficialis frame at the upper limb of insulation component, and adjacent insulation component forms another support to overlap adjacent ramus superficialis frame when assembling, and seals thereby form lapping (shiplap).The level of this vinyl plate and insulation component and vertical edge are configured to overlap when mounted.
US 6,277, and 915 have described block chlorinated polyolefins, and it is disclosed as the haloflex impact modifier in the performance enhancers of high rubber graft copolymer or PVC and/or the CPVC resin.Compare with random chloridized polyolefin with the processing aid in being commonly used for PVC or CPVC as impact modifier, this block chlorinated polyolefins (for example block chlorinated polyethylene) provides the fine dispersion of this impact modifier particle in matrix, and better bonding between impact modifier and PVC and/or the CPVC interface, thereby provide better physical property, as the impact strength that records by Notched Izod.Compare with random chloridized polyolefin, compatible with this impact modifier or PVC/CPVC with the nature difference that block chlorinated polyolefins is realized owing to polyolefinic each the independent block of this block, thus cause better bonding between the phase.
US 2005/0153122 has described the weather-proof external application building products of high temperature goods.Goods as wallboard, cabinet finiss, paving, fence and roofing product and so on are made by CPVC layer and the optional insulating barrier that pastes on this CPVC layer.This product has and is higher than 180 °F, preferably is higher than 205 heat distortion temperature.These goods can be with the dark color manufacturings and are had the direct daylight that is enough to bear in the temperature climate and a hear resistance of reverberation.
US 2005/0208247 has described the multilayer pipe of making by main body outside co-extrusion inlay section thermal plastic copolyester elastomer (COPE) on the outer surface of the endless tube core (it has 0.95 millimeter (38 mil) wall thickness that radially records to 1.375 millimeters (55 mils)) of CPVC/PVC with random length and cross section.In this COPE poly-be adhered to the coextensive toroidal cores of the whole substantially length of this pipe on.Although this COPE when contacting with water easy degraded and CPVC and CPVC and the blend that is less than 25 weight %PVC at co-extrusion hard normally during for pipe, the COPE with the appointment wall thickness that in laminated tube, meets the circuit design standard (SDR-11 of the U.S.) that comes into force and overall size have with commercially available CPVC with the laminated tube of CPVC/PVC and manage (its be individual layer but not laminate) essentially identical performance characteristic.
None relates to the permanent melt bonded method to hard polyvinyl chloride composition of thermoplastic elastomer (TPE) that makes above-mentioned patent.Therefore, still need to provide wherein thermoplastic elastomer (TPE) co-extrusion and permanent adhesive to the suprabasil goods of RPVC, composite and laminate in the prior art.
Summary of the invention
The present invention relates to melt bonded multilayer materials, it comprises: (a) one deck comprises the thermoplastic elastomer (TPE) of 50 to the 100 weight % that account for the said composition gross weight and the composition for thermoplastic elastomer of the adhesion promotor of 0 to the 50 weight % that accounts for the said composition gross weight at least; (b) one deck rigid polyvinyl chloride polymer compositions at least.
The invention still further relates to melt bonded multilayer materials, it comprises: (a) comprise by the thermoplastic elastomer (TPE) of 50 to the 100 weight % that account for the said composition gross weight and account for the ground floor of the composition for thermoplastic elastomer that the adhesion promotor of 0 to 50 weight % of said composition gross weight constitutes; (b) between described first and second layers and bonding described first and second layers at least one tack coat that comprises adhesive composition (tie layer); (c) comprise the second layer of rigid polyvinyl chloride polymer compositions.
The invention further relates to melt bonded multilayer materials, it comprises: (a) comprise the thermoplastic elastomer (TPE) of 50 to the 100 weight % that account for the said composition gross weight and the ground floor of the foamed thermoplastic elastomer composition of the adhesion promotor of 0 to the 50 weight % that accounts for the said composition gross weight; (b) comprise the second layer of rigid polyvinyl chloride polymer compositions.
Accompanying drawing describes in detail
Fig. 1 (a) and (b) be schematic diagram according to melt bonded composite of the present invention.
Fig. 2 is the schematic diagram according to melt bonded die head of the present invention.
Fig. 3 is the schematic diagram according to multilayer materials of the present invention in building occupancy.
Fig. 4 is the schematic diagram according to multilayer materials of the present invention in building occupancy.
Detailed Description Of The Invention
As detailed below with reference to the preferred embodiments of the invention and the embodiment that wherein comprises is more readily understood the present invention.
Before this compound of disclosure and description, composition, goods and/or method, it being understood that to the invention is not restricted to specific synthetic method, special process or specific device, therefore variable certainly.Also it being understood that term used herein only to be used to describe specific embodiments and nonrestrictive.
At following specification with in claims, can mention many terms, they should be designated as has following meanings.
Unless indicate separately clearly in the literary composition, singulative " ", " a kind of ", " being somebody's turn to do " used in this specification and the appended claims comprise plural object.Therefore, for example, when mentioning a polymer, comprise one or more polymer.
Scope can be expressed as in this article since a particular value, and/or arrives till another particular value.When showing this scope, another embodiment comprises from this particular value and beginning and/or till another particular value.Similarly, when using this antecedent, it being understood that this particular value constitutes another embodiment as approximate table registration value.The end points that it being understood that each scope not only with other end spot correlation ground but also effective independently with another end points.In addition, the scope described in the disclosure and claims is intended to clearly comprise gamut and end points not only.For example, 0 to 10 the scope of being described to is intended to disclose all integers between 0 and 10, and for example 1,2,3,4 or the like, all marks between 0 and 10, for example 1.5,2.3,4.57,6.1113 or the like and end points 0 and 10.In addition, with chemical substituting group, be intended to clearly comprise and disclose C1 and C5 hydrocarbon and C2, C3 and C4 hydrocarbon as " C1 to C5 hydrocarbon " relevant scope.
" optional " or " randomly " is meant that incident or the situation described thereafter may take place or may not take place, and this description comprises situation that described incident or situation take place and situation about not taking place.For example, word " optional heat " is meant that this material may be heated or not heat, and this word not only comprises the method for heating but also comprise the method that does not heat.
Unless indicate separately, all numerical value that are expressed as component, character (as molecular weight), reaction condition etc. used in this specification and claims are understood that to be modified by this term in all cases.Correspondingly, unless make opposite indication, the numerical parameter of setting forth in following specification and the appended claims is the approximation that possible become with the required character that the present invention attempts to obtain.At least, each numerical parameter should be explained according to the number of the significant digits of being reported and by using the common technology of rounding off at least.Be similar to although set forth the number range and the parameter of broad range of the present invention, the numerical value of listing in the specific embodiment as far as possible accurately provides.But any numerical value all contains some error that the standard deviation that exists in its experimental measurement separately must cause inherently.
In application in the whole text, when mentioning patent or publication, the disclosure of these lists of references with on the degree that the contained argumentation of this paper conflicts is not quoted through this and is incorporated the application in full at them, thus the prior art situation in field under more abundant description the present invention.
The present invention relates to melt bonded at the bottom of the hard alkylene thermoplastic elastomer (TPE) on (as RPVC).In some embodiments of the present invention, this thermoplastic elastomer (TPE) can contain and the compatible adhesion promotor in the polyolefin-based end of hard.Perhaps, in some embodiments, this thermoplastic elastomer (TPE) can extrude and use compatible tack coat permanent adhesive to the RPVC substrate.In other embodiments, this thermoplastic elastomer (TPE) be can extrude and permanent adhesive to the suprabasil froth bed of RPVC.
For example, in an embodiment as shown in Fig. 1 (a), a kind of melt bonded multilayer materials 10 is provided, and it comprises at least one deck and comprises the composition for thermoplastic elastomer 12 of thermoplastic elastomer (TPE) and adhesion promotor and one deck rigid polyvinyl chloride polymer compositions 14 at least.
Fig. 1 b has shown the composite 10 according to one embodiment of the invention, and it comprises melt bonded TPE layer 12 on hard PVC layer 14 and optional tack coat 16.
Any adhesion promotor all is useful in the composition for thermoplastic elastomer of the present invention.This adhesion promotor can be that any independent adhesion promotor or its can be the blends of one or more adhesion promotors.The adhesion promotor that is suitable for comprises, for example, and the maleinization polyolefin; Chloridized polyolefin; The maleinization chloridized polyolefin; Acrylate copolymer; Ionomer; Hydrocarbon resin comprises aliphatic resin (C5), aromatic resin (C9) and alicyclic resin (DCPD), as
(can available from Eastman Chemical); Rosin and rosin resins derived therefrom, as
And Poly-
(can available from Eastman Chemical), terpene resin; Low-molecular-weight resin, as
With
(can available from EastmanChemical), vinyl-acrylate copolymer, as ethylene methyl acrylate copolymer (EMAC) or ethylene butyl acrylate copolymer (EBAC) (can available from Westlake), vinyl-vinyl acetate copolymer (EVA), as
(can available from DuPont), and copolyester elastomer (COPE), as
With
(can available from Eastman Chemical).
Usually, this composition for thermoplastic elastomer comprises the thermoplastic elastomer (TPE) and the adhesion promotor that accounts for 0 to 50 weight % of said composition gross weight of 50 to the 100 weight % that account for the said composition gross weight.For example account for 75 to 95% of said composition gross weight, or the thermoplastic elastomer (TPE) of 80 to 90 weight % and account for 5 to 25% of said composition gross weight, or the adhesion promotor of 10 to 20 weight %.
Randomly, in one embodiment, between TPE layer 12 and PVC layer 14, comprise optional tack coat 16.Should be used for PVC layer 14 being bondd or being adhered to TPE layer 12 by optional tack coat 16.According to the present invention, this optional tack coat 16 comprises adhesive composition.Usually, this adhesive composition can be that any independent adhesion promotor or its can be the blends of one or more adhesion promotors.The adhesion promotor that is suitable for comprises, for example, and the maleinization polyolefin; Chloridized polyolefin; The maleinization chloridized polyolefin; Acrylate copolymer; Ionomer; Hydrocarbon resin comprises aliphatic resin (C5), aromatic resin (C9) and alicyclic resin (DCPD), as
(can available from Eastman Chemical); Rosin and rosin resins derived therefrom, as
And Poly-
(can available from Eastman Chemical), terpene resin; Low-molecular-weight resin, as
With
(can available from EastmanChemical), vinyl-acrylate copolymer, as ethylene methyl acrylate copolymer (EMAC) or ethylene butyl acrylate copolymer (EBAC) (can available from Westlake), vinyl-vinyl acetate copolymer (EVA), as
(can available from DuPont), and copolyester elastomer (COPE), as
With
(can available from Eastman Chemical).
For example, in one embodiment, this adhesive composition can comprise the styrene block copolymer of 25 to 75 weight %, COPE and the polyacrylic blend of 0 to 5 weight % of 25 to 75 weight %.In another embodiment, this adhesive composition can comprise the styrene block copolymer of 25 to 75 weight %, EVA and the polyacrylic blend of 0 to 5 weight % of 25 to 75 weight %.In an embodiment again, this adhesive composition can comprise EVA and the polyacrylic blend of 0 to 5 weight % of TPV, 25 to the 75 weight % of 25 to 75 weight %.In addition, in some embodiments, this optional tack coat 16 can comprise the blend of adhesion promotor and thermoplastic elastomer (TPE).
In the present invention, this multilayer materials 10 can have any desired thickness of suitable desired use.In one embodiment, this TPE layer 12 can have 5.0 inches thickness at the most, and this hard PVC layer 14 can have 5.0 inches thickness at the most, and tack coat 16 can have 0.2 inch thickness at the most.For example, in some purposes, this TPE layer 12 can have 0.05 inch to 5.0 inches thickness, and hard PVC layer 14 can have 0.05 inch to 5.0 inches thickness, and tack coat 16 can have 0.005 inch to 0.2 inch thickness.As further example, in other purposes, this TPE layer 12 can have 0.05 to 1.0 inch thickness, and hard PVC layer 14 can have 0.05 inch to 1.0 inches thickness, and tack coat 16 can have 0.005 inch to 0.1 inch thickness.
In addition, can select bonding strength between TPE layer 12 and the hard PVC layer 14 to adapt to desired use.Randomly, in some purposes,, can obtain higher bonding strength by comprising optional tack coat 16.For example, in some embodiments, the bonding strength between TPE layer 12 and the hard PVC layer 14 is higher than 5pli (pound/linear inch).In some embodiments, bonding strength is up to 10pli.In other embodiments, the bonding strength between TPE layer and the hard PVC layer is 5pli to 10pli.
One embodiment of the invention as shown in Figure 3 relate to the multilayer materials of extruding 30, and it comprises: the ground floor 32 that contains foamed thermoplastic elastomer composition; With the second layer 34 that contains polyvinyl chloride polymer compositions.Choose wantonly in some embodiments, can comprise aforesaid tack coat.In addition, Fig. 4 has shown the composite 40 according to one embodiment of the invention as the goods in the building occupancy, and it comprises melt bonded foaming TPE layer 42 to hard PVC layer 44.
For example, an embodiment comprises melt bonded multilayer materials, and it has the thermoplastic elastomer (TPE) that comprises 50 to the 100 weight % that account for the said composition gross weight and accounts for the ground floor 32 or 42 of foamed thermoplastic elastomer composition of adhesion promotor of 0 to 50 weight % of said composition gross weight; With the second layer 34 or 44 that comprises rigid polyvinyl chloride polymer compositions.
According to one embodiment of the invention, composite 30 or 40 comprises the ground floor 32 or 42 of melt bonded foamed thermoplastic elastomer composition on hard PVC layer 34 or 44.The thermoplastic elastomer (TPE) of this foaming comprises thermoplastic elastomer (TPE) and adhesion promotor usually.Suitably, above-mentioned any thermoplastic elastomer (TPE) and any adhesion promotor all are suitable for.For example, suitable thermoplastic elastomer (TPE) comprises copolyester elastomer (COPE), as PET (poly-(PETP)) and PBT (poly-(terephthalic acid (TPA) 1,4-fourth diester)) elastomer (can be used as Hytrel (R) available from DuPont Company and as Riteflex (R) available from Ticona Company), or PCCE present cycloaliphatic polyesters (1,4-cyclohexane diacid, 1, the copolymer of 4-cyclohexanedimethanol and polytetramethylene glycol) (can be used as
With
Available from Eastman Chemical).
This thermoplastic elastomer (TPE) froth bed 32 or 42 can use any conventional method foaming.Can use any traditional chemical or physical blowing agent.Preferably, this blowing agent is a physical blowing agent, as the mixture of carbon dioxide, ethane, propane, normal butane, iso-butane, pentane, hexane, butadiene, acetone, carrene, any CFC, HCFC or hydrogen fluorohydrocarbon and previous materials.
This blowing agent can mix with thermoplastic elastomer (TPE) to realize the required degrees of expansion in the gained foam with any aequum.Usually, based on 100 weight portion thermoplastic elastomer (TPE)s, this blowing agent can add in the thermoplastic elastomer (TPE) with the amount of 0.5 to 80 weight portion.More preferably, this blowing agent is with per 100 weight portion thermoplastic elastomer (TPE)s 1 to 30, and most preferably 2 to 15 parts amount exists.
If desired or necessary, also can comprise various additives with thermoplastic elastomer (TPE).For example, it may be desirable comprising nucleator (for example zinc oxide, zirconia, silica, talcum etc.) and/or aging modifier (for example fatty acid ester, fatty acid amide, hydroxyl acid amides etc.).Other additive that can comprise if desired, is pigment, colouring agent, filler, antioxidant, fire retardant, stabilizing agent, essence, mask agent and analog.
According to foam of the present invention preferably by extrusion molding manufacturing well known in the art.Can use the extruder of any traditional type, for example single screw rod, twin-screw and/or series connection extruder.In extruder, with this thermoplastic elastomer (TPE) fusion and mixing.In the elastomer of fusion, add blowing agent via the one or more injection ports in the extruder.Used any additives can add in the molten elastomer in extruder and/or can add with elastomer.This extruder pushed away the die head of extruder end with whole melt blend (elastomer of fusion, blowing agent and any additives) and pushed the zone of the temperature and pressure (comparing with the temperature and pressure in the extruder) with reduction.Usually, the zone with temperature and pressure of reduction is an ambiance.Abrupt pressure reduction makes the blowing agent nucleation and expand into many holes, and they solidified, thus blowing agent is trapped in the hole in polymer cooling (because temperature descends) time.
For example, in one embodiment, use nitrogen blowing agent, under 380 ° to 395 roughly melt temperature, extrude PCCE (Neostar FN006) elastomer of Eastman Chemical supply.The use of nitrogen reduces by 0.1 to 0.15 proportion with the density of PCCE melt-flow.Can control the proportion reduction of fusion PCCE by the speed of introducing the nitrogen in the melt-flow with the high precision infusion pump.
Be not limited by any theory, be pressed under the land area intrinsic pressure of die head together PCCE and PVC between at the interface, realize the chemical adhesion of PCCE and PVC via coextruding heat.This instrument provides transition gradually (rail that goes out via machining) thereby merges the intersection surface of PCCE and PVC with any composite design.The major diameter of these two kinds of materials (L/D) is than producing suitable shear rate condition to plasticate and each polymer of fusion.Usually, 24: the compression ratio of 1L/D extruder is 2.5 to 1 (minimums).Two kinds of materials all use the gravity feeding hopper to be fed into independently in the screw/barrel combination to arrive the rear end of this screw rod.By standard " cooling mist " and standard H by the shower nozzle supply
2The cooling at the PCCE of fusion co-extrusion behind the die head to the hard PVC is carried out in the combination of O cooling bath.
Generally speaking, the elastomeric density of PCCE (final proportion) that foams via four principal element control nitrogen:
1. enter the mass velocity of the nitrogen of PCCE melt-flow
2.PCCE melt temperature
3.PCCE shear rate
4. the particular die design that comprises the expection swelling (just outside die face) of suitable land area and foaming PCCE.
In some embodiments, froth bed is the blend that constitutes by the polymer by PCCE and another type that said method foams.
Any hard polyvinylchloride resin all is suitable in the present invention.According to the present invention can with polyvinyl chloride polymer comprise " Vinyl Chloride Polymers " entry of Kirk-OthmerEncyclopedia of Chemical Technology, the 24th volume, the 4th edition, those described in (1997) the 1017-1053 pages or leaves (it is incorporated herein by this reference).For example, can use vinyl chloride resin suitably in the present invention, as the copolymer of ryuron, vinyl chloride and other vinyl monomer, they homopolymers halogenated compound and with the mixture or the blend of other plastics.As further example, in the hard polyolefin layer, can use weather-proof polyvinyl chloride (PVC), as
With
(can available from PolyOne).
In addition, according to the present invention can with the PVC polymer comprise ryuron and have the repetitive that at least 70 weight % are become by polymerization of vinyl choride monomer, or at least 80 weight % or at least 90 weight % or even those chloroethylene polymerization resins of 95 weight % or the repetitive that more becomes by polymerization of vinyl choride monomer.
Polychloroethylene composition of the present invention can comprise the repetitive by polymerization of vinyl choride monomer one-tenth, and also can comprise the comonomer of 30 weight % at the most that accounts for this copolymer, it is selected from, but be not limited to, following one or more: acrylate, for example methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, acrylic acid cyanogen ethyl ester and analog; Vinyl esters is as vinyl acetate and propionate; Methacrylate is as methacrylic acid stuffing, EMA, hydroxy-ethyl acrylate, butyl methacrylate and analog; Nitrile is as acrylonitrile and methacrylonitrile; Acrylamide is as Methacrylamide, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide and analog; Halogen-containing vinyl monomer is as vinylidene chloride, vinylidene fluoride and bromine ethene; Vinyl ethers is as ethyl vinyl ether, chloroethyl vinyl ethers and analog; Vinyl ketone, styrene derivative comprise AMS, vinyltoluene, chlorostyrene; Vinyl naphthalene; Alkene is as ethene, butylene, isobutene, propylene and hexene; And has suitable reactivity with vinyl chloride and for other copolymerisable monomer well known by persons skilled in the art or monomer mixture.
Embodiments more of the present invention can be used the PVC blend that contains crosslinked PVC and independent crosslinked PVC.The crosslinked PVC polymer can be as United States Patent(USP) Nos. 4,755,699 and 5, instruction is by making chloroethylene polymerization manufacturing in 248,546 (its relevant portion is incorporated herein by this reference) in the presence of cross-linking monomer (as above-mentioned diallyl phthalate, trimethylolpropane triacrylate, allyl methacrylate and analog).
Described homopolymers and copolymer can be buied and can make by any suitable polymerization (comprising suspension, dispersion or blend).For example, the polyvinyl chloride polymer that uses suspension method to make is suitable in the present invention.
When we said that PVC composition of the present invention is hard, we were meant, for example, said composition is to contain small amount of plasticizer or not plasticizer-containing unmodified or the not PVC of plasticizing.And flexible or the plasticizing PVC can comprise the plasticizer that is higher than 12phr usually.Therefore, hard PVC of the present invention is characterised in that to have than the hot strength level that is classified as flexible modified PVC combination object height.
In addition, according to the present invention, hard PVC is meant the character of the given compound with specific stretch modulus.For example, PVC has above 10 at it
5Be characterized as being hard during the stretch modulus of psi (or 689MPa), drop on 3x10 in its stretch modulus
3To 10
5Be characterized as being semi-rigid in the time of between the psi (20.7MPa), have less than 3x10 at it
3Be characterized as being flexible (tensile modulus values is based on the standard A STM condition of 23 ℃ and 50% relative humidity) during the stretch modulus of psi (or 20.7MPa).Therefore, hard PVC of the present invention can have the tensile modulus values that changes in wide region, and for example, this tensile modulus values can be 800MPa to 1000MPa, or 1000MPa to 2000MPa or even reach 3000MPa or higher.
Melt bonded multilayer materials of the present invention can use any conventional method manufacturing by any traditional handicraft, for example comprise extrude, injection moulding, calendering, blowing, rotational molding or vacuum mo(u)lding.
Melt bonded multilayer materials of the present invention can be used as the goods in the following purposes: building and structure, transportation (comprising motor vehicle and airborne vehicle), the consumer goods, industrial equipment and machinery, utensil, ornament and accessory, sports goods, utensil, packing, health care and electronic device.For example, melt bonded multilayer materials of the present invention can be used for making the goods that are used for following purposes: the backing of PVC plate and sealant; Door and window (window and door fenestrations); PVC conveyer belt external grid layer; Door and window slip strip of paper used for sealing; The door and window mine dam; Seal with pvc pipe.Usually, the goods of being made by composite of the present invention provide improved durability, energy efficiency, more high-quality, improved weatherability, comprise solar heat protection, wet and UV protection.
Further illustration the present invention of the following example that can be by its preferred embodiment is although unless it being understood that separately and indicate that these embodiment only are used to illustrate rather than will limit the scope of the invention.
Embodiment
Embodiment 1
Be prepared as follows co-extrusion PVC/PCCE goods:
Material:
Hard layer: 100%Georgia Gulf 7181 Weatherable 7181 PVC
Flexible backing:
97.5%Eastman
FN007 PCCE elastomer
2.5%Phoenix Plastics Cel-span 840 blowing agents
Use following process conditions:
Hard layer: 3.5 " Davis Standard Thermatic extruder, L/D=24: 1
Zone 1-5,330 °F
1,340 in mould district
2,360 in mould district
Flexible back sheet: Berlyn 1 ", L/D=24: 1
1,360 in zone
2,395 in zone
3,410 in zone
Cross-over pipe, 415 °F
Die head, 440 °F
It is 0.050 that this hard die head is made nominal wall thickness " wide PVC planomural fragment, it simulates traditional dwelling house vinyl plate cross section approx.With 0.250 " thickness extrusion foaming flexible layers.Use Pyncnometry to determine that the bubble content of PCCE flexible layers is 30% void level.This flexible foaming PCCE layer can not be peeled off from the hard PVC layer.
Comparative Examples 2
Hard PVC fragment used according to the invention and flexible TPE fragment are according to following method and condition manufacturing contrast co-extrusion PVC/TPE goods.
Material:
Hard layer: 100%Georgia Gulf 7181 Weatherable 7181 PVC
Flexible layers: 100%Santoprene 201-45 thermoplastic vulcanizate
Use die head co-extrusion and the shape layer shown in Fig. 2.Die head 20 among Fig. 2 has hard PVC layer 24, adhesive layer 26 and TPE layer 22.According to the instrument of Fig. 2 be designed to or do not use with optional tack coat.For Comparative Examples 2, do not use optional tack coat.
Use following process conditions:
Hard layer: 3.5 " Davis Standard Thermatic extruder, L/D=24: 1
Zone 1-5,330 °F
1,340 in mould district
2,360 in mould district
Flexible back sheet: Berlyn 1 ", L/D=24: 1
1,345 in zone
2,360 in zone
3,365 in zone
Cross-over pipe, 370 °F
Die head, 370 °F
Comparative Examples 3
Make the co-extrusion goods according to the program identical with Comparative Examples 2.But in Comparative Examples 3, the TPE layer is a 100%GLS Dynaflex G7960 SBS compound.
Embodiment 4
According to the program identical with Comparative Examples 2 with form and make co-extrusion PVC/TPE goods, but used TPE is with 15 weight %Eastman Eastotac 142W hydrocarbon resin modifications among the embodiment 4.The TPV compound of modification uses Werner ﹠amp; The Pfleiderer corotation changes double screw extruder, 30 mm dias, 42 " length, 400 °F, melt blended under 300rpm.
Embodiment 5
According to the program identical with form and make co-extrusion PVC/TPE goods, but in embodiment 5, use optional tack coat with Comparative Examples 2.Should constitute by 50 weight %Kraton G-1660SEBS, 45 weight %Eastman Epolene G-3015 resins and 5 weight %Marlex, 120 polypropylene by optional tack coat.Should use Werner ﹠amp by optional tack coat compound; The Pfleiderer corotation changes double screw extruder, 30 mm dias, 42 " length, 400 °F, melt blended under 300rpm.
Use the Instron testing machine under 12rpm, to use 180 ° of disbonded tests to measure the bonding strength of co-extrusion goods according to ASTM D-3330.The value of being reported is 5 mean values of measuring.
Table 1.180 ° peel strength
| Peel strength (psi) | s.d. | |
| Comparative Examples 2 | No bonding | N/A |
| Comparative Examples 3 | 7.6 | 2.7 |
| Embodiment 4 | 8.3 | 1.2 |
| Embodiment 5 | 11.3 | 2.4 |
Such as in the table 1 summary, the TPEs of modification shows improved melt bonded intensity via co-extrusion and PVC composite according to the present invention.In addition, PCCE polyester thermoplastic elastomer and PVC form melt bonded composite, and it produces than strong bonding of substrate.Composite article of the present invention can easily also extensively be used in the multiple use via the extrusion molding preparation.
Described the present invention with reference to its preferred embodiment especially, but it being understood that and to make change within the spirit and scope of the present invention and revise.
Claims (31)
1. melt bonded multilayer materials, it comprises:
(a) one deck composition for thermoplastic elastomer at least, said composition comprises
(i) account for the said composition gross weight 50 to 100 weight % thermoplastic elastomer (TPE) and
(ii) account for the adhesion promotor of 0 to 50 weight % of said composition gross weight; With
(b) one deck rigid polyvinyl chloride polymer compositions at least.
2. melt bonded multilayer materials, it comprises:
(a) comprise the ground floor of composition for thermoplastic elastomer, said composition comprises
(i) account for the said composition gross weight 50 to 100 weight % thermoplastic elastomer (TPE) and
(ii) account for the adhesion promotor of 0 to 50 weight % of said composition gross weight;
(b) between described first and second layers and bonding described first and second layers at least one tack coat that comprises adhesive composition; With
(c) comprise the second layer of rigid polyvinyl chloride polymer compositions.
3. melt bonded multilayer materials, it comprises:
(a) ground floor of foamed thermoplastic elastomer composition, said composition comprises
(i) account for the said composition gross weight 50 to 100 weight % thermoplastic elastomer (TPE) and
(ii) account for the adhesion promotor of 0 to 50 weight % of said composition gross weight; With
(b) comprise the second layer of rigid polyvinyl chloride polymer compositions.
4. claim 1,2 or 3 multilayer materials, wherein this composition for thermoplastic elastomer comprises
(i) account for the said composition gross weight 80 to 99 weight % thermoplastic elastomer (TPE) and
(ii) account for the adhesion promotor of 1 to 20 weight % of said composition gross weight.
5. claim 1,2 or 3 multilayer materials, wherein this composition for thermoplastic elastomer comprises
(i) account for the said composition gross weight 85 weight % thermoplastic elastomer (TPE) and
(ii) account for the adhesion promotor of 15 weight % of said composition gross weight.
6. claim 1,2 or 3 multilayer materials, wherein this thermoplastic elastomer (TPE) is one or more in styrene block copolymer, thermoplastic vulcanizate (TPV), copolyester elastomer (COPE), polyolefin elastomer (POE) or the TPUE (TPU).
7. the multilayer materials of claim 6, wherein styrene block copolymer is one or more in s-B-S (SBS), styrene-isoprene-phenylethene (SIS), styrene-ethylene-butylene-styrene (SEBS) or the styrene-ethylene-propylene-styrene (SEPS).
8. the multilayer materials of claim 6, wherein thermoplastic vulcanizate is one or more in polypropylene or the ethylene propylene diene monomer rubber.
9. the multilayer materials of claim 3, wherein this foamed thermoplastic composition comprises copolyester elastomer (COPE), as PET (poly-(PETP)), PBT (poly-(terephthalic acid (TPA) 1,4-fourth diester)) elastomer or PCCE (present cycloaliphatic polyesters).
10. the multilayer materials of claim 3 further is included between described first and second layers and bonding described first and second layers at least one tack coat that comprises adhesive composition.
11. claim 1,2 or 3 multilayer materials, wherein this adhesion promotor is the maleinization polyolefin; Chloridized polyolefin; The maleinization chloridized polyolefin; Acrylate copolymer; Ionomer; Vinyl-acrylate copolymer is as ethylene methyl acrylate copolymer (EMAC) and ethylene butyl acrylate copolymer (EBAC); Hydrocarbon resin is as aliphatic resin (C5), aromatic resin (C9) or alicyclic resin (DCPD); Rosin and rosin resins derived therefrom; Terpene resin; Low-molecular-weight resin; Vinyl-vinyl acetate copolymer (EVA); Or in the copolyester elastomer (COPE) one or more.
12. the multilayer materials of claim 2 or 10, wherein this adhesive composition comprises the maleinization polyolefin; Chloridized polyolefin; The maleinization chloridized polyolefin; Acrylate copolymer; Ionomer; Vinyl-acrylate copolymer is as ethylene methyl acrylate copolymer (EMAC) and ethylene butyl acrylate copolymer (EBAC); Hydrocarbon resin is as aliphatic resin (C5), aromatic resin (C9) or alicyclic resin (DCPD); Rosin and rosin resins derived therefrom; Terpene resin; Low-molecular-weight resin; Vinyl-vinyl acetate copolymer (EVA); Or in the copolyester elastomer (COPE) one or more.
13. the multilayer materials of claim 2 or 10, wherein this adhesive composition is one or more in vinyl-vinyl acetate copolymer (EVA) or the copolyester elastomer (COPE).
14. the multilayer materials of claim 2 or 10, wherein this adhesive composition comprises 25 to 75 weight % styrene block copolymers, 25 to 75 weight %COPE and the polyacrylic blend of 0 to 5 weight %.
15. the multilayer materials of claim 2 or 10, wherein this adhesive composition comprises 25 to 75 weight % styrene block copolymers, 25 to 75 weight %EVA and the polyacrylic blend of 0 to 5 weight %.
16. the multilayer materials of claim 2 or 10, wherein this adhesive composition comprises 25 to 75 weight %TPV, 25 to 75 weight %EVA and the polyacrylic blend of 0 to 5 weight %.
17. the multilayer materials of claim 2 or 10, wherein this adhesive composition comprises the blend of adhesion promotor and thermoplastic elastomer (TPE).
18. the multilayer materials of claim 2 or 3, wherein the thickness of ground floor is that the thickness of 5.0 inches and the second layer at the most is 5.0 inches at the most.
19. the multilayer materials of claim 2 or 3, wherein the thickness of ground floor is that the thickness of 0.05 inch to 5.0 inches and the second layer is 0.05 inch to 5.0 inches.
20. the multilayer materials of claim 2 or 3, wherein the thickness of ground floor is that the thickness of 0.05 inch to 1.0 inches and the second layer is 0.05 inch to 1.0 inches.
21. the multilayer materials of claim 2 or 10, wherein the thickness of optional tack coat is 0.005 inch to 0.1 inch.
22. the multilayer materials of claim 2 or 10, wherein the thickness of optional tack coat is 0.005 inch to 0.2 inch.
23. the multilayer materials of claim 2 or 10, wherein the thickness of optional tack coat is 0.2 inch at the most.
24. the multilayer materials of claim 2 or 3, the bonding strength between wherein said first and second layers is higher than 5pli.
25. the multilayer materials of claim 2 or 3, the bonding strength between wherein said first and second layers is 10pli at the most.
26. the MULTILAYER COMPOSITE goods of claim 2 or 3, the bonding strength between wherein said first and second layers is 5pli to 10pli.
27. comprise the goods of claim 1,2 or 3 multilayer materials.
28. claim 1,2 or 3 multilayer materials, wherein this composite is used to make the goods in the following purposes: the backing of PVC plate and sealant; Door and window; PVC conveyer belt external grid layer; Door and window slip strip of paper used for sealing; The door and window mine dam; The pvc pipe envelope.
29. claim 1,2 or 3 melt bonded multilayer materials, wherein this composite is used to make the goods in the following purposes: building and structure, the transportation that comprises motor vehicle and airborne vehicle, the consumer goods, industrial equipment and machinery, utensil, ornament and accessory, sports goods, utensil, packing, health care or electronic device.
30. claim 1,2 or 3 melt bonded multilayer materials, it is melt bonded that wherein this composite uses one or more following methods: extrude, injection moulding, calendering, blowing, rotational molding or vacuum mo(u)lding.
31. melt bonded method according to claim 1,2 or 3 multilayer materials.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US89849007P | 2007-01-31 | 2007-01-31 | |
| US60/898,490 | 2007-01-31 | ||
| US60/923,589 | 2007-04-16 | ||
| US12/021,350 | 2008-01-29 |
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| Publication Number | Publication Date |
|---|---|
| CN101600568A true CN101600568A (en) | 2009-12-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008800037278A Pending CN101600568A (en) | 2007-01-31 | 2008-01-31 | Rigid pvc melt bonded thermoplastic elastomer composite material |
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| CN (1) | CN101600568A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147560A (en) * | 2013-03-15 | 2013-06-12 | 浙江华夏杰高分子建材有限公司 | Floor system |
| CN104769028A (en) * | 2012-03-30 | 2015-07-08 | 莫塞尔挤出有限责任公司 | Method of forming polymeric foam and related foam articles |
| CN106836733A (en) * | 2017-03-31 | 2017-06-13 | 河北鸣仁橡胶制品有限公司 | A kind of rubber laminated floor and preparation method thereof |
| CN113321881A (en) * | 2021-06-15 | 2021-08-31 | 东营瑞致新材料有限公司 | PVC foam used as offshore buoyancy material and preparation method thereof |
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2008
- 2008-01-31 CN CNA2008800037278A patent/CN101600568A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104769028A (en) * | 2012-03-30 | 2015-07-08 | 莫塞尔挤出有限责任公司 | Method of forming polymeric foam and related foam articles |
| US11292163B2 (en) | 2012-03-30 | 2022-04-05 | Mucell Extrusion, Llc | Method of forming polymeric foam and related foam articles |
| CN103147560A (en) * | 2013-03-15 | 2013-06-12 | 浙江华夏杰高分子建材有限公司 | Floor system |
| CN106836733A (en) * | 2017-03-31 | 2017-06-13 | 河北鸣仁橡胶制品有限公司 | A kind of rubber laminated floor and preparation method thereof |
| CN113321881A (en) * | 2021-06-15 | 2021-08-31 | 东营瑞致新材料有限公司 | PVC foam used as offshore buoyancy material and preparation method thereof |
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Application publication date: 20091209 |