CA2010236A1 - Hot plastisol compositions - Google Patents
Hot plastisol compositionsInfo
- Publication number
- CA2010236A1 CA2010236A1 CA 2010236 CA2010236A CA2010236A1 CA 2010236 A1 CA2010236 A1 CA 2010236A1 CA 2010236 CA2010236 CA 2010236 CA 2010236 A CA2010236 A CA 2010236A CA 2010236 A1 CA2010236 A1 CA 2010236A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- resin
- vinyl acetate
- vinyl
- plasticizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 140
- 229920001944 Plastisol Polymers 0.000 title claims abstract description 29
- 239000004999 plastisol Substances 0.000 title claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- 239000004014 plasticizer Substances 0.000 claims abstract description 37
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 28
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 19
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 19
- 239000002952 polymeric resin Substances 0.000 claims abstract description 18
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 15
- 239000013466 adhesive and sealant Substances 0.000 claims abstract description 13
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 10
- 239000001993 wax Substances 0.000 claims abstract description 10
- 239000000049 pigment Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000000080 wetting agent Substances 0.000 claims abstract description 8
- 230000009969 flowable effect Effects 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 22
- 150000002148 esters Chemical class 0.000 claims description 18
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 15
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002318 adhesion promoter Substances 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 15
- -1 oleyl nitride Chemical class 0.000 claims description 14
- 239000004952 Polyamide Substances 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 229920002647 polyamide Polymers 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 12
- 150000008064 anhydrides Chemical class 0.000 claims description 12
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000003973 paint Substances 0.000 claims description 11
- 229920001519 homopolymer Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 150000001282 organosilanes Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid group Chemical group C(CCCCC)(=O)O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 8
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical group CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 6
- 230000000712 assembly Effects 0.000 claims description 6
- 238000000429 assembly Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- 229920001289 polyvinyl ether Polymers 0.000 claims description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical group C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 2
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- FGTVYMTUTYLLQR-UHFFFAOYSA-N n-ethyl-1-phenylmethanesulfonamide Chemical compound CCNS(=O)(=O)CC1=CC=CC=C1 FGTVYMTUTYLLQR-UHFFFAOYSA-N 0.000 claims description 2
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 3
- 239000011118 polyvinyl acetate Substances 0.000 claims 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- FFSJSGNXYKUSCQ-UHFFFAOYSA-N [2,2,4-trimethyl-1-(2-methylpropanoyloxy)pentan-3-yl] benzoate Chemical compound CC(C)C(=O)OCC(C)(C)C(C(C)C)OC(=O)C1=CC=CC=C1 FFSJSGNXYKUSCQ-UHFFFAOYSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
- 239000004615 ingredient Substances 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 description 19
- 230000001070 adhesive effect Effects 0.000 description 19
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 239000000565 sealant Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 5
- 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 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- XFDQLDNQZFOAFK-UHFFFAOYSA-N 2-benzoyloxyethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOC(=O)C1=CC=CC=C1 XFDQLDNQZFOAFK-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008029 phthalate plasticizer Substances 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- AHGFXGSMYLFWEC-UHFFFAOYSA-N [SiH4].CC(=C)C(O)=O Chemical compound [SiH4].CC(=C)C(O)=O AHGFXGSMYLFWEC-UHFFFAOYSA-N 0.000 description 1
- SLETZFVTVXVPLS-UHFFFAOYSA-N [Zn].[Cd].[Ba] Chemical compound [Zn].[Cd].[Ba] SLETZFVTVXVPLS-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- LGDWWNMEEOHPNZ-UHFFFAOYSA-N buta-1,3-diene;ethenyl acetate;styrene Chemical compound C=CC=C.CC(=O)OC=C.C=CC1=CC=CC=C1 LGDWWNMEEOHPNZ-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- AEPUKSBIJZXFCI-UHFFFAOYSA-N dibenzyl nonanedioate Chemical compound C=1C=CC=CC=1COC(=O)CCCCCCCC(=O)OCC1=CC=CC=C1 AEPUKSBIJZXFCI-UHFFFAOYSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- FFPZYKQFAKXVSW-UHFFFAOYSA-N didecyl pentanedioate Chemical compound CCCCCCCCCCOC(=O)CCCC(=O)OCCCCCCCCCC FFPZYKQFAKXVSW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical compound CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002922 epistatic effect Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XPOXIRBXYPGDNE-UHFFFAOYSA-N methanediamine Chemical compound N[CH]N XPOXIRBXYPGDNE-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WCLDITPGPXSPGV-UHFFFAOYSA-N tricamba Chemical compound COC1=C(Cl)C=C(Cl)C(Cl)=C1C(O)=O WCLDITPGPXSPGV-UHFFFAOYSA-N 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Abstract of Disclosure Thermally stable hot applied plastisol compositions are especially useful in the assembly of metal parts. The compositions have adhesive and sealant qualities which allow them to be used in automotive assembly plants. Compositions of the invention comprise as major ingredients finely divided polyvinyl chloride resin, plasticizer, thermoplastic polymeric resin which is solid at room temperature but softens to a flowable state at application temperature, and an adhesion promotion system. Optionally a filler, wax, heat stabilizer, pigment, wetting agent, or mixtures thereof may be added.
The individual components work synergistically to get good application properties, metal adhesion, wash-out resistance, and paintability.
The individual components work synergistically to get good application properties, metal adhesion, wash-out resistance, and paintability.
Description
-` -1- 2~236 ''' HOT PLASTISOL COMPOSITIONS
Backaround of the Invention This invention relates to plastisol compositions. More particularly the invention relates to thermally stable plastisol compositions which are capable of being hot applied to metal surfaces for adhesive and sealant purposes.
Adhesive and sealant compositions are widely used in many commercial and industrial production processes. A
multitude of such compositions have been developed over the years, many of which were designed for a special use.
Adhesive compositions generally are used to bind two substrates together. Sealant compositions generally are used to form a load-bearing elastic joint between two substrates. The sealants also exclude dirt, moisture and other materials from the joint and form a smooth juncture at the joint. Necessarily, there is~some overlap in the functions of the adhesive and sealant compositions.
The automotive industry is a major user of both ~-adhesive and sealant compo~sitions. Automobiles are assembled from several structural components. ~The components are joined together in various fashlons depending on the particular components and the degree of stress that will have to be endured. For certain assembly steps an adhesive composition applied as a liquid and ~ subsequently hardened provides sufficlent bonding strength. For example, metal assemblies of door panels, quarter panels, tailgates, and roofs use adhesive compo~sitions. These same assemblies also use sealant ~-compositions at a~late~r stage in the assembly line. Still 30~ ~other~automobile assemblies which are~welded or bolted together~use sealant compositions in their seams. The ~ . ~
:
:.: ::: ` :': ''. . ' ,; ~ . .... ; : . , 201(~23~
wheel house, shock tower, rocker panel, firewall, floor hem flange, floorpan, and trunk are a few examples of where sealants, but not adhesives, are used.
Typical automobile body assembly lines contain a separate body shop and paint shop areas where adhesives and sealants are individually used in each area respectively. Adhesive compositions applied in the body shop area are normally high strength epoxy or modified-epoxy adhesives which are capable of bonding to oily galvanized steel. In some cases vinyl plastisols are employed, however, these applications are normally limited to situations that do not require high bonding performance. In any case, these materials are applied at room temperature and later cured through exposure to heat. A current weakness of these materials is that in order to apply them, they must be of low enough viscosity to be mechanically pumped with adequate flow rates.
Normally, because of their low viscosity these materials are easily displaced when exposed to liquid impingement by various cleaning solutions (washes) to which the assembly body parts are exposed.
Recently a new class of materials referred to as curing hot applied adhesives have been introduced in the automotive body shop. These are urethane or epoxy-modified urethanes and are solid or semi-solid at room temperature. These adhesives function by changing from a flowable fluid at an elevated application temperature to a bonding solid at use temperature. The hot applied adhesives have a number of characteristics -30 which make them attractive for use in the body shop area. -They are usually solvent free and thus no special fume - collection hoods are needed. They have low viscosities when made fluid and thus flow readily to fill gaps and wet the substrates to be bonded. Most importantly the resins ~- ~' - ' ' ~ ' ' ~1~6 after application provide a high strength bond and cure to an even higher strength after passage through drying ovens at a later stage on the line. Additionally, the applied adhesive compositions have a rapid set time. They will not be displaced when exposed to liquid impingement by various washes and electrophoretic priming fluids to which the assembled body parts are subjected.
The assemblied parts as they move from the body shop area are subjected to sealing, painting, and final oven curing in the paint shop area. Sealant compositions used in this area must also have a certain set of characteristics to be acceptable. Vinyl plastisol compositions have been found to have those needed characteristics. Basically, a vinyl plastisol is a finely divided polyvinyl chloride resin suspended in a plasticizer. The plastisols are liquids which are applied -at room temperature to the substrate. The liquid is converted to a solid through exposure to heat. In effect, the heat causes the suspended resin particles to be fused or dissolved in the plasticizer. A solid product results upon subsequent cooling.
Vinyl plastisols are excellent as sealants in the paint shop area of the body assembly line. They flow readily at room temperature to fill seams and body joints which need to be sealed. They adhere well to primed metal surfaces. They can be painted over without leaching or causing other cosmetic problems. Finally, they are durable enough to withstand normal weather and user exposure. Another important quality of the vinyl plastisols is that they are not expensive. The plastisols would ideally be used in all adhesive and sealing phases of the automotive assembly process if they had better ~, :
. .. `'.. '. . ... ' , ` :: ' . ':':: ' . : : : .
_4- 2Q~6 metal bonding properties and could withstand the washes and primer applications experienced in the body shop area of the process.
Accordingly, a need exists for a product with both strong adhesive and excellent sealant properties and for compositions which combine the characteristics of both the curing hot applied adhesives and the vinyl plastisols. -Summary of the Invention That need is met by the present invention which provides a thermally stable hot applied plastisol composition. That composition has a host of qualities :
which makes it attractive for bonding and/or sealing - -joints areas in metal assemblies such as automobile bodies and parts thereof.
The hot applied thermally stable plastisol -composition of the present invention comprises as a principal component thereof from about 20~ to about 35% of -a finely divided polyvinyl chloride resin. The composition preferably contains a mixture of two polyvinyl chloride resins which comprise about 23-32% and most preferably about 25-30% of the composition. The first resin may be a homopolymer dispersion resin with inherent viscosity of about 1.00 ml/g and is preferably between 50 and 100% and most preferably between 50% and 75~ of the resin system. The second resin is a blending resin that may be a copolymer of vinyl chloride and maleic ester with inherent viscosity of about .97 ml/g and is preferably between 0 and 50% and most preferably between 25% and 50% ~
of the resin system. ~ -'" ''- .
- ~ ': ' ' ': : : ' ' ~ . , _5_ 2Q~3~
A second major component of the present composition is from about 15% to about 35% of a plasticizer. The plasticizer is preferably diisodecyl phthalate and preferably is about 19-30% and most preferably about 22-30% of the composition.
Also included is about 2-25% of a thermoplastic polymeric resin, preferably about 5-20% and most preferably about 10-15% of a vinyl acetate/ethylene copolymer having a vinyl acetate content preferably of about 50-70% and most preferably about 60-65%.
Finally there is present about 3-15% of an adhesion promotion system. The adhesion promotion system preferably comprises about 5-13~ and most preferably about 5-11% of the total composition. The adhesion promotion ~ ;
system preferably contains an unsaturated organosilane (between about 0.1 and 1%), an acrylic monomer (between 2 and 8%), an unsaturated acid or anhydride monomer (between -0.1 and 2%) an epoxy or modified epoxy resin (between 0.5 and 4%) and a hardening agent for the eposy resin, such as a polyamide (between 1 and 5%).
Optionally the composition also contains filler, waxes, heat stabilizers, pigment, wetting agents and various combinations and mixtures thereof.
The composition of the present invention has both adhesive and sealant characteristics which make it especially useful in the assembly of metal automotive parts. The plastisol composition of the present invention is thermally stable, can be hot applied to automotive parts for adhesive and sealant purposes, and can subsequently withstand the successive steps of a primer application, primer wash-off, top coat paint application and oven bake.
~ ~ .
~ , .
-6- 20~Z.~, The preferred method of bonding and/or sealing using the present composition involves hot applying the plastisol composition to joint areas of a metal assembly, followed by cooling the composition sufficiently to achieve sufficient bonding. If an automobile body or a part thereof is being sealed in this manner, the method may in some instances further involve applying a primer composition to the metal assembly, heating the metal assembly to cure the primer, and applying additional plastisol composition to joint areas to form a sealed smooth surface. In any event, it will usually involve applying a paint composition to the metal assembly, and baking the metal assembly to cure the plastisol i -composition and the paint composition.
Accordingly, it is an object of the present invention to provide a hot applied thermally stable - -plastisol composition having adhesive and sealant qualities useful in the assembly of automobile bodies, and to a method of bonding and/or sealing joint areas in metal assemblies using such a composition. Other objects and advantages of the invention will become apparent from the following detailed description and the appended claims.
Detailed Descri~tion of the Invention As mentioned the composition of the present invention comprises as major ingredients finely divided polyvinyl chloride resin, plasticizer, thermoplastic polymeric resin and an adhesion promotion system. Each of the individual components of the composition will be discussed in detail as well as the composition's mode of use. All percentages and ratios are by weight unless otherwise stated.
. , , . .,. . , .: , : ~, . ; .. , ,: . .
_7_ 2~ 3~, Polyvinyl chloride resins used in the compositions of this invention are finely divided resin -particles which are capable of being dispersed in a plasticizer. The resins are well known and have been widely used in plastisol compositions. The polyvinyl chloride resins include polymers of vinyl chloride as well as copolymers of vinyl chloride with copolymerizable vinyl addition monomers. Examples of such vinyl addition monomers include vinyl acetate, the vinyl acetals, maleic esters, styrene, vinylidene chloride and acrylonitrile.
The particularly preferred polyvinyl chloride resins are the fine particle dispersion type homopolymer resins and vinyl chloride/maleic ester copolymers in a monomer weight ratio of vinyl chloride to maleic ester of from about 99:1 to about 90:10. Blends of several different polyvinyl chloride resins may also be used and will also be referred to as the polyvinyl chloride resin, even though more than one resin may actually be present. Actually, as mentioned, a blend of 50-100~ and most preferably 50-75%
of a homopolymer dispersion resin and 0-50% and most preferably 25-50% of a vinyl chloride/maleic ester copolymer blending resin is preferred.
Plasticizers useful in the present invention include monomeric types selected to achieve desired characteristics such as proper gelation, fusion, and flow properties. Examples of such monomeric plasticizers include monomeric esters of phthalic, benzoic, succinic, adipic, sebacic, talic, lauric, azelaic, caprylic, hexanoic, phosphoric, oleic, glutaric, trimellitic and stearic acids. Specific plasticizers include dioctyl phthalate, ethylene glycol dibenzoate, dioctyl succinate, dibutyl sebacate; dibenzyl azelate; didecyl glutarate and ~ -similar compounds. Other monomeric plasticizers include :, ~ :: ~ .: .. . . . . , ,.. :.: . " . : . :, ., . ,: ~. . :
Backaround of the Invention This invention relates to plastisol compositions. More particularly the invention relates to thermally stable plastisol compositions which are capable of being hot applied to metal surfaces for adhesive and sealant purposes.
Adhesive and sealant compositions are widely used in many commercial and industrial production processes. A
multitude of such compositions have been developed over the years, many of which were designed for a special use.
Adhesive compositions generally are used to bind two substrates together. Sealant compositions generally are used to form a load-bearing elastic joint between two substrates. The sealants also exclude dirt, moisture and other materials from the joint and form a smooth juncture at the joint. Necessarily, there is~some overlap in the functions of the adhesive and sealant compositions.
The automotive industry is a major user of both ~-adhesive and sealant compo~sitions. Automobiles are assembled from several structural components. ~The components are joined together in various fashlons depending on the particular components and the degree of stress that will have to be endured. For certain assembly steps an adhesive composition applied as a liquid and ~ subsequently hardened provides sufficlent bonding strength. For example, metal assemblies of door panels, quarter panels, tailgates, and roofs use adhesive compo~sitions. These same assemblies also use sealant ~-compositions at a~late~r stage in the assembly line. Still 30~ ~other~automobile assemblies which are~welded or bolted together~use sealant compositions in their seams. The ~ . ~
:
:.: ::: ` :': ''. . ' ,; ~ . .... ; : . , 201(~23~
wheel house, shock tower, rocker panel, firewall, floor hem flange, floorpan, and trunk are a few examples of where sealants, but not adhesives, are used.
Typical automobile body assembly lines contain a separate body shop and paint shop areas where adhesives and sealants are individually used in each area respectively. Adhesive compositions applied in the body shop area are normally high strength epoxy or modified-epoxy adhesives which are capable of bonding to oily galvanized steel. In some cases vinyl plastisols are employed, however, these applications are normally limited to situations that do not require high bonding performance. In any case, these materials are applied at room temperature and later cured through exposure to heat. A current weakness of these materials is that in order to apply them, they must be of low enough viscosity to be mechanically pumped with adequate flow rates.
Normally, because of their low viscosity these materials are easily displaced when exposed to liquid impingement by various cleaning solutions (washes) to which the assembly body parts are exposed.
Recently a new class of materials referred to as curing hot applied adhesives have been introduced in the automotive body shop. These are urethane or epoxy-modified urethanes and are solid or semi-solid at room temperature. These adhesives function by changing from a flowable fluid at an elevated application temperature to a bonding solid at use temperature. The hot applied adhesives have a number of characteristics -30 which make them attractive for use in the body shop area. -They are usually solvent free and thus no special fume - collection hoods are needed. They have low viscosities when made fluid and thus flow readily to fill gaps and wet the substrates to be bonded. Most importantly the resins ~- ~' - ' ' ~ ' ' ~1~6 after application provide a high strength bond and cure to an even higher strength after passage through drying ovens at a later stage on the line. Additionally, the applied adhesive compositions have a rapid set time. They will not be displaced when exposed to liquid impingement by various washes and electrophoretic priming fluids to which the assembled body parts are subjected.
The assemblied parts as they move from the body shop area are subjected to sealing, painting, and final oven curing in the paint shop area. Sealant compositions used in this area must also have a certain set of characteristics to be acceptable. Vinyl plastisol compositions have been found to have those needed characteristics. Basically, a vinyl plastisol is a finely divided polyvinyl chloride resin suspended in a plasticizer. The plastisols are liquids which are applied -at room temperature to the substrate. The liquid is converted to a solid through exposure to heat. In effect, the heat causes the suspended resin particles to be fused or dissolved in the plasticizer. A solid product results upon subsequent cooling.
Vinyl plastisols are excellent as sealants in the paint shop area of the body assembly line. They flow readily at room temperature to fill seams and body joints which need to be sealed. They adhere well to primed metal surfaces. They can be painted over without leaching or causing other cosmetic problems. Finally, they are durable enough to withstand normal weather and user exposure. Another important quality of the vinyl plastisols is that they are not expensive. The plastisols would ideally be used in all adhesive and sealing phases of the automotive assembly process if they had better ~, :
. .. `'.. '. . ... ' , ` :: ' . ':':: ' . : : : .
_4- 2Q~6 metal bonding properties and could withstand the washes and primer applications experienced in the body shop area of the process.
Accordingly, a need exists for a product with both strong adhesive and excellent sealant properties and for compositions which combine the characteristics of both the curing hot applied adhesives and the vinyl plastisols. -Summary of the Invention That need is met by the present invention which provides a thermally stable hot applied plastisol composition. That composition has a host of qualities :
which makes it attractive for bonding and/or sealing - -joints areas in metal assemblies such as automobile bodies and parts thereof.
The hot applied thermally stable plastisol -composition of the present invention comprises as a principal component thereof from about 20~ to about 35% of -a finely divided polyvinyl chloride resin. The composition preferably contains a mixture of two polyvinyl chloride resins which comprise about 23-32% and most preferably about 25-30% of the composition. The first resin may be a homopolymer dispersion resin with inherent viscosity of about 1.00 ml/g and is preferably between 50 and 100% and most preferably between 50% and 75~ of the resin system. The second resin is a blending resin that may be a copolymer of vinyl chloride and maleic ester with inherent viscosity of about .97 ml/g and is preferably between 0 and 50% and most preferably between 25% and 50% ~
of the resin system. ~ -'" ''- .
- ~ ': ' ' ': : : ' ' ~ . , _5_ 2Q~3~
A second major component of the present composition is from about 15% to about 35% of a plasticizer. The plasticizer is preferably diisodecyl phthalate and preferably is about 19-30% and most preferably about 22-30% of the composition.
Also included is about 2-25% of a thermoplastic polymeric resin, preferably about 5-20% and most preferably about 10-15% of a vinyl acetate/ethylene copolymer having a vinyl acetate content preferably of about 50-70% and most preferably about 60-65%.
Finally there is present about 3-15% of an adhesion promotion system. The adhesion promotion system preferably comprises about 5-13~ and most preferably about 5-11% of the total composition. The adhesion promotion ~ ;
system preferably contains an unsaturated organosilane (between about 0.1 and 1%), an acrylic monomer (between 2 and 8%), an unsaturated acid or anhydride monomer (between -0.1 and 2%) an epoxy or modified epoxy resin (between 0.5 and 4%) and a hardening agent for the eposy resin, such as a polyamide (between 1 and 5%).
Optionally the composition also contains filler, waxes, heat stabilizers, pigment, wetting agents and various combinations and mixtures thereof.
The composition of the present invention has both adhesive and sealant characteristics which make it especially useful in the assembly of metal automotive parts. The plastisol composition of the present invention is thermally stable, can be hot applied to automotive parts for adhesive and sealant purposes, and can subsequently withstand the successive steps of a primer application, primer wash-off, top coat paint application and oven bake.
~ ~ .
~ , .
-6- 20~Z.~, The preferred method of bonding and/or sealing using the present composition involves hot applying the plastisol composition to joint areas of a metal assembly, followed by cooling the composition sufficiently to achieve sufficient bonding. If an automobile body or a part thereof is being sealed in this manner, the method may in some instances further involve applying a primer composition to the metal assembly, heating the metal assembly to cure the primer, and applying additional plastisol composition to joint areas to form a sealed smooth surface. In any event, it will usually involve applying a paint composition to the metal assembly, and baking the metal assembly to cure the plastisol i -composition and the paint composition.
Accordingly, it is an object of the present invention to provide a hot applied thermally stable - -plastisol composition having adhesive and sealant qualities useful in the assembly of automobile bodies, and to a method of bonding and/or sealing joint areas in metal assemblies using such a composition. Other objects and advantages of the invention will become apparent from the following detailed description and the appended claims.
Detailed Descri~tion of the Invention As mentioned the composition of the present invention comprises as major ingredients finely divided polyvinyl chloride resin, plasticizer, thermoplastic polymeric resin and an adhesion promotion system. Each of the individual components of the composition will be discussed in detail as well as the composition's mode of use. All percentages and ratios are by weight unless otherwise stated.
. , , . .,. . , .: , : ~, . ; .. , ,: . .
_7_ 2~ 3~, Polyvinyl chloride resins used in the compositions of this invention are finely divided resin -particles which are capable of being dispersed in a plasticizer. The resins are well known and have been widely used in plastisol compositions. The polyvinyl chloride resins include polymers of vinyl chloride as well as copolymers of vinyl chloride with copolymerizable vinyl addition monomers. Examples of such vinyl addition monomers include vinyl acetate, the vinyl acetals, maleic esters, styrene, vinylidene chloride and acrylonitrile.
The particularly preferred polyvinyl chloride resins are the fine particle dispersion type homopolymer resins and vinyl chloride/maleic ester copolymers in a monomer weight ratio of vinyl chloride to maleic ester of from about 99:1 to about 90:10. Blends of several different polyvinyl chloride resins may also be used and will also be referred to as the polyvinyl chloride resin, even though more than one resin may actually be present. Actually, as mentioned, a blend of 50-100~ and most preferably 50-75%
of a homopolymer dispersion resin and 0-50% and most preferably 25-50% of a vinyl chloride/maleic ester copolymer blending resin is preferred.
Plasticizers useful in the present invention include monomeric types selected to achieve desired characteristics such as proper gelation, fusion, and flow properties. Examples of such monomeric plasticizers include monomeric esters of phthalic, benzoic, succinic, adipic, sebacic, talic, lauric, azelaic, caprylic, hexanoic, phosphoric, oleic, glutaric, trimellitic and stearic acids. Specific plasticizers include dioctyl phthalate, ethylene glycol dibenzoate, dioctyl succinate, dibutyl sebacate; dibenzyl azelate; didecyl glutarate and ~ -similar compounds. Other monomeric plasticizers include :, ~ :: ~ .: .. . . . . , ,.. :.: . " . : . :, ., . ,: ~. . :
2~23~, :
esters of 2, 2, 4-trimethyl-1,3-pentanediol, citric acid esters and n-ethyl toluenesulfonamide. Preferred is diisodecyl phthalate.
Polymeric plasticizing agents can be used in conjunction with the monomeric plasticizers in order to achieve special characteristics such as permanence, weathering resistance, and especially paintability.
Polymer plasticizers useful in the present invention include the higher molecular weight polymeric acid esters ~molecular weights greater than 1000). Examples of these polymeric plasticizers include esters of succinic, adipic, sebacic, talic, lauric, azelaic, caprylic, hexanoic, benzoic, phthalic, phosphoric, oleic, glutaric, trimellitic, and stearic acids, including mixtures or blends of these compounds. The polymeric plasticizers have low diffusion rates because of their higher molecular ;
weights and also act to retard the migration of other components from the applied compositions. Additionally, low molecular weight chlorinated paraffinic oils and epoxidized soybean oil can be used as a co-plasticizers.
Again, blends of several different plasticizers may be used, but will be referred to simply as the plasticizer.
A third essential component of the compositions is a thermoplastic polymeric resin which is capable of softening at application temperatures sufficiently to be -flowable. Resins of this nature are commonly referred to as hot applied resins. The resins are characterized by their ability to set to a solid material by cooling rather than by solvent evaporation or chemical reaction. Thus, the resins are reduced to a soft or molten state by inc~easing temeprature. Most of these resins ':. ' 2t3~ 3fi progressively soften over a wide temperature range, though some may actually have very narrow melting ranges and become a true liquid. Each type of resin is useful herein and is referred to as a hot applied resin. Typical resins are solid or semi-solid pastes at room temperature with softening temperatures of about 200F to about 375F.
Examples of thermoplastic polymeric resins include the polyethylenes, polyamides, polyvinyl butyrals, polyvinyl acetates, cellulose derivatives, polyesters, polymethyl methacrylates and ethacrylates, polyvinyl ethers and polyurethanes. Specific examples of such thermoplastic resins include ethylene ethyl acrylate copolymers, vinyl acetate styrene butadiene block copolymers and butyl rubber.
Preferred thermoplastic resins are those polymers that show solubility and compatibility with polyvinyl chloride polymers such as ethylene vinyl acetate, vinyl acetate ethylene, vinyl acetate, acrylonitrile, acrylonitrile butadiene copolymer, chlorinated ethylene vinyl acetate, polyepsilon caprolactone, methyl metacrylate and polybutylene terephthalate. An ethylene vinyl acetate having a 20-80% vinyl acetate content is preferred. Vinyl acetate ethylene copolymers having a vinyl acetate content of preferably 50-70% and most preferably 60-65% are highly preferred because of their ` -balance of compatibility, flow, adhesion and flexibility.
~ he adhesion promotion system found in the current compositions preferably contains an unsaturated organosilane; an acrylic monomer; and an unsaturated acid or anhydride monomer. Most preferably it also contains an epoxy resin or modified epoxy resin and a hardening agent 2~
--1 0-- ' ' for the epoxy resin, such as a polyamide or modified polyamide. All of the unsaturated materials are capable of polymerization with peroxide initiation and heat. The formation of a highly functionalized oligomeric or polymeric modified acrylic species in situ (after heating) in concert with the reacted epoxy resin presumably is what is responsible for the tenacious bonding of the current adhesive to oily metals.
Examples of unsaturated organosilanes are the vinyl, acrylics and methacrylic types such as vinyl trichlorosilane, vinyl triethoxy silane, vinyl trimethoxy silane, vinyl-tris B-methoxy-ethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxy propyl-tris-2 (methoxy-ethoxy) silane and vinyl triacetoxy silane. Examples of acrylic monomers are any of the free radical induced polymerizable mono or multifunctional acrylic or methacrylic monomers such as trimethalopropane trimethacrylate, hexane diol diacrylate, and butyl methacrylate. Examples of unsaturated acid or anhydride .
monomers are the vinyl, acrylic, and methacrylic mono or poly functional acid or anhydride materials maleic, acrylic, crotonic, methacrylic, oleic, linoleic, and tetrahydrophthalic acid or anhydride.
Examples of unmodified epoxy resins are those based on bisphenol-A and epichlorohydrin with typical properties that includes an epoxy value of 152-155 equiv./lOOg and a weight per epoxide of 182-192. Other typical epoxy resins are phenol novolac, triphenylolmethane, and tetrabromo bis-A. An example of a modified epoxy resin includes the preferred elastomeric modified liquid epoxy resin which is a 40~ ~dduct of carboxylated acrylonitrile butadiene elastomer and a liquid bisphenol-A and epichlorohydrin type epoxy. That adduct has a weight per epoxide of 325-375. Curing ~. . .
11 2~n23~
for the epoxy or modified epoxy resin is accomplished by reacting the resin with an appropriate curing or hardening agent. Typical hardening agents a polyamides, diethylenetriamine, methane diamine, m-phenylene diamine, diaminodiphenyl sulfone, tris (dimethyl amino methyl) phenol, dicyandiamide, BF3-monoethyl amine and nadicmethyl anhydride. Preferred is a modified polyamide hardening agent such as a latent polyamide dispersion which is an adduct of phthalic anhydride and diethylenetriamine in an unmodified liquid epoxy resin. The epoxy or modified epoxy resin~hardening age~t system apparently modifies the galvanized surface by reacting with and/or to the adhesion ~ :
promotion system in the preferred embodiment.
It has been found that inclusion of the adhesion promotion system in the compositions at the stated level significantly increases the adhesion of the composition to a metal surface without adversely affecting the qualities of the applied composition. That is, the composition's resistance to primer wash, paintability, viscosity stability etc. are not adversely affected by the adhesion promoter. Other adhesion promoters are also preferably used with the current materials and, again, reference to the adhesion promoter is reference to the adhesion promoter system unless otherwise indicated.
The compositions of the invention are formulated with the above essential components to achieve a product having the desired set of characteristics considering their intended use. The composition is intended as an -adhesive and sealant for use in the assembly of metal automotive parts. As such the compositions are able to flow at application temperature with the proper wet-out onto a surface, i.e., they are "pumpable". Upon cooling an initial degree of adhesion is attained as discussed below. Additionally, because of the intended use, the set ' ' .
': ' . ' ' ' ' ' ' : : :~ .: : ", ', -12- 20~
composition is capable of receiving a primer wash without experiencing wash-out. Finally, the composition is able to accept a primer and top coat paint and also to withstand multiple oven bakes. The composition also has a final degree of adhesion which is very durable.
Optional components of the composition of the invention comprise waxes, heat stabilizers, fillers, --pigments, and wetting agents. Such components are readily available. Amorphous waxes, carnauba wax, castor oil wax and various synthetic waxes was useful. Examples of heat ;
stabilizers include lead and barium- cadmium-zinc systems. Fillers include ground and precipitated calcium carbonate, ground silica, clays and talcs. Examples of ;~
wetting agents are polyethylene glycol derivatives. -~
Compositions of the invention with the immediately aforedescribed qualities comprise (a) from about 20% to about 35% of the finely divided polyvin~l chloride resin, (b) from about 15% to about 35% of the plasticizer, (c) from about 2% to about 25% of the thermoplastic po~ymeric resin, and (d) from about 3% to ~ -about 15% of the adhesion promotion system. A preferred composition consists essentially ~a) from about 23% to about 32% of the polyvinyl chloride resin, (b) from about lg% to about 30% of the plasticizer, (c) from about 5% to -about 20% of the thermoplastic polymeric resin, (d) from about 5% to about 13% of adhesion promoter, and (e) the balance selected from the group consisting of a wax, heat stabilizer, filler, pigment, wetting agent, and mixtures thereof.
A particularly preferred composition in terms of performance and cost considerations consists essentially ~ -of (a) from about 25% to about 30% of the polyvinyl chloride resin, (b) from about 22% to about 30% of a plasticizer, (c) from about 10% to about 15% of the :
20~
thermoplastic polymeric resin, (d) from about 5% to about 11% of adhesion promoter, (e) from about 15% to about 20%
of a filler, (f) from about 0% to about 8% wax, and (g) from about 1% to about 4% of a heat stabilizer The aforedescribed compositions of the invention are unique in their ability to act as a structural adhesive and a sealant in the assembly of automotive bodies. Thus, the compositions are used in the body area of the assembly to bond various steel components such as hoods and roof panels. Additionally, the compositions are used in the body shop area where certain components which demand greater structural bonds as obtained by welding require a sealant to smooth over the weld. The compositions are heated from about 90F to about 160F and applied in any convenient manner, such as pumping, troweling, flowing! brushing or spraying. The compositions are thermally stable so that they can be heated and drawn from by a pumping operation for prolonged periods. Upon cooling the compositions harden to a state with an initial degree of adhesion which is adequate for the intended purpose. This solidification occurs depite the plastisol nature of the compositions.
The assembled automotive body components or body shell is next prepared for painting. Typically this involves phosphate cleaning, washing, immersing the body shell in a primer bath, applying an electric charge to effect electrodeposition of the primer to the body shell, and removing the primed body shell from the bath. The compositions originally applied as adhesives and sealants 30~ rémain in tack. That is, they are not washed out onto adioining surface areas of the body shell.
Subsequent to the priming step, if one is used, and prior to an oven bake, the body shell is top coated with a paint and oven baked to a totally cured state by . .
- .
: ~ ' - .... . .. . .. . , ., , ~.; . . ;:, . .
2~
plastisol fusion of the sealer and also the top coat paint. The fusion temperature is well above the -aforementioned application temperature. The applied compositions of the invention are also able to withstand these operations without causing cosmetic-type problems such as discoloration, tackiness, cracking, etc. -It should be apparent the compositions of the invention enjoy all the qualities of previously used hot applied adhesive compositions and vinyl plastisol compositions, collectively. The synergistic nature of the composition components without adverse properties is very unexpected. An added benefit flowing from one composition having such qualities is reduced inventory in not having to stock two separate products as well as a consequent 15 reduced administrative burden. -The following examples illustrate the invention.
: ~ , , . ~ . ,., , ,, . ~; ............ , : :, -', ` ' ` ` :,: . ' : i , .. ..... .. . . . .
-15- 20102~ :
Example I
A preferred thermally stable hot applied plastisol composition has the following formulation:
% , .
Polyvinyl chloride dispersion resin (1) 19 .00 Polyvinyl chloride blending resin (2)8.00 Diisodecyl phthalate plasticizer 28.00 Epoxidized soybean oil plasticizer (3) 2.00 10 Vinyl acetate ethylene copolymer thermoplastic resin (4) 13.00 3-methacryloxypropyl trimethoxy silane adhesion promoter (5) 0.30 Elastomeric modified liquid epoxy resin (6) 2.00 15 Calcium organic thixotropic agent (7) 0.50 Methacrylate ester adhesion promoter (8) 4.~0 Calcium carbonate filler (9) 8.04 Hydrophobic fumed silica filler (10)8.00 Calcium oxide filler 2.00 20 Anionic surfactant wetting agent (11) 0.16 Modified polyamide hardening agent (12) : 3.0 Cumene hydroperoxide 0.08 Tri-basic lead sulfate heat stabilizer (13) 1.00 Hydroquinone monomethyl ether 0.02 25 Tetrahydrophthalic anhydride adhesion promoter 0.30 Carbon black pigment 0.05 Titanium dioxide pigment 0.05 100 . 00 ~13 A homopolymer available from Huls Corp. as Vestolit .
(2) A copolymer of vinyl chloride and dibutyl maleate available from The Goodyear Tire and Rubber Co. as Pliovic MC-85 (3) Available from the C.P. Hall Co. as PlastHall ESO
esters of 2, 2, 4-trimethyl-1,3-pentanediol, citric acid esters and n-ethyl toluenesulfonamide. Preferred is diisodecyl phthalate.
Polymeric plasticizing agents can be used in conjunction with the monomeric plasticizers in order to achieve special characteristics such as permanence, weathering resistance, and especially paintability.
Polymer plasticizers useful in the present invention include the higher molecular weight polymeric acid esters ~molecular weights greater than 1000). Examples of these polymeric plasticizers include esters of succinic, adipic, sebacic, talic, lauric, azelaic, caprylic, hexanoic, benzoic, phthalic, phosphoric, oleic, glutaric, trimellitic, and stearic acids, including mixtures or blends of these compounds. The polymeric plasticizers have low diffusion rates because of their higher molecular ;
weights and also act to retard the migration of other components from the applied compositions. Additionally, low molecular weight chlorinated paraffinic oils and epoxidized soybean oil can be used as a co-plasticizers.
Again, blends of several different plasticizers may be used, but will be referred to simply as the plasticizer.
A third essential component of the compositions is a thermoplastic polymeric resin which is capable of softening at application temperatures sufficiently to be -flowable. Resins of this nature are commonly referred to as hot applied resins. The resins are characterized by their ability to set to a solid material by cooling rather than by solvent evaporation or chemical reaction. Thus, the resins are reduced to a soft or molten state by inc~easing temeprature. Most of these resins ':. ' 2t3~ 3fi progressively soften over a wide temperature range, though some may actually have very narrow melting ranges and become a true liquid. Each type of resin is useful herein and is referred to as a hot applied resin. Typical resins are solid or semi-solid pastes at room temperature with softening temperatures of about 200F to about 375F.
Examples of thermoplastic polymeric resins include the polyethylenes, polyamides, polyvinyl butyrals, polyvinyl acetates, cellulose derivatives, polyesters, polymethyl methacrylates and ethacrylates, polyvinyl ethers and polyurethanes. Specific examples of such thermoplastic resins include ethylene ethyl acrylate copolymers, vinyl acetate styrene butadiene block copolymers and butyl rubber.
Preferred thermoplastic resins are those polymers that show solubility and compatibility with polyvinyl chloride polymers such as ethylene vinyl acetate, vinyl acetate ethylene, vinyl acetate, acrylonitrile, acrylonitrile butadiene copolymer, chlorinated ethylene vinyl acetate, polyepsilon caprolactone, methyl metacrylate and polybutylene terephthalate. An ethylene vinyl acetate having a 20-80% vinyl acetate content is preferred. Vinyl acetate ethylene copolymers having a vinyl acetate content of preferably 50-70% and most preferably 60-65% are highly preferred because of their ` -balance of compatibility, flow, adhesion and flexibility.
~ he adhesion promotion system found in the current compositions preferably contains an unsaturated organosilane; an acrylic monomer; and an unsaturated acid or anhydride monomer. Most preferably it also contains an epoxy resin or modified epoxy resin and a hardening agent 2~
--1 0-- ' ' for the epoxy resin, such as a polyamide or modified polyamide. All of the unsaturated materials are capable of polymerization with peroxide initiation and heat. The formation of a highly functionalized oligomeric or polymeric modified acrylic species in situ (after heating) in concert with the reacted epoxy resin presumably is what is responsible for the tenacious bonding of the current adhesive to oily metals.
Examples of unsaturated organosilanes are the vinyl, acrylics and methacrylic types such as vinyl trichlorosilane, vinyl triethoxy silane, vinyl trimethoxy silane, vinyl-tris B-methoxy-ethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxy propyl-tris-2 (methoxy-ethoxy) silane and vinyl triacetoxy silane. Examples of acrylic monomers are any of the free radical induced polymerizable mono or multifunctional acrylic or methacrylic monomers such as trimethalopropane trimethacrylate, hexane diol diacrylate, and butyl methacrylate. Examples of unsaturated acid or anhydride .
monomers are the vinyl, acrylic, and methacrylic mono or poly functional acid or anhydride materials maleic, acrylic, crotonic, methacrylic, oleic, linoleic, and tetrahydrophthalic acid or anhydride.
Examples of unmodified epoxy resins are those based on bisphenol-A and epichlorohydrin with typical properties that includes an epoxy value of 152-155 equiv./lOOg and a weight per epoxide of 182-192. Other typical epoxy resins are phenol novolac, triphenylolmethane, and tetrabromo bis-A. An example of a modified epoxy resin includes the preferred elastomeric modified liquid epoxy resin which is a 40~ ~dduct of carboxylated acrylonitrile butadiene elastomer and a liquid bisphenol-A and epichlorohydrin type epoxy. That adduct has a weight per epoxide of 325-375. Curing ~. . .
11 2~n23~
for the epoxy or modified epoxy resin is accomplished by reacting the resin with an appropriate curing or hardening agent. Typical hardening agents a polyamides, diethylenetriamine, methane diamine, m-phenylene diamine, diaminodiphenyl sulfone, tris (dimethyl amino methyl) phenol, dicyandiamide, BF3-monoethyl amine and nadicmethyl anhydride. Preferred is a modified polyamide hardening agent such as a latent polyamide dispersion which is an adduct of phthalic anhydride and diethylenetriamine in an unmodified liquid epoxy resin. The epoxy or modified epoxy resin~hardening age~t system apparently modifies the galvanized surface by reacting with and/or to the adhesion ~ :
promotion system in the preferred embodiment.
It has been found that inclusion of the adhesion promotion system in the compositions at the stated level significantly increases the adhesion of the composition to a metal surface without adversely affecting the qualities of the applied composition. That is, the composition's resistance to primer wash, paintability, viscosity stability etc. are not adversely affected by the adhesion promoter. Other adhesion promoters are also preferably used with the current materials and, again, reference to the adhesion promoter is reference to the adhesion promoter system unless otherwise indicated.
The compositions of the invention are formulated with the above essential components to achieve a product having the desired set of characteristics considering their intended use. The composition is intended as an -adhesive and sealant for use in the assembly of metal automotive parts. As such the compositions are able to flow at application temperature with the proper wet-out onto a surface, i.e., they are "pumpable". Upon cooling an initial degree of adhesion is attained as discussed below. Additionally, because of the intended use, the set ' ' .
': ' . ' ' ' ' ' ' : : :~ .: : ", ', -12- 20~
composition is capable of receiving a primer wash without experiencing wash-out. Finally, the composition is able to accept a primer and top coat paint and also to withstand multiple oven bakes. The composition also has a final degree of adhesion which is very durable.
Optional components of the composition of the invention comprise waxes, heat stabilizers, fillers, --pigments, and wetting agents. Such components are readily available. Amorphous waxes, carnauba wax, castor oil wax and various synthetic waxes was useful. Examples of heat ;
stabilizers include lead and barium- cadmium-zinc systems. Fillers include ground and precipitated calcium carbonate, ground silica, clays and talcs. Examples of ;~
wetting agents are polyethylene glycol derivatives. -~
Compositions of the invention with the immediately aforedescribed qualities comprise (a) from about 20% to about 35% of the finely divided polyvin~l chloride resin, (b) from about 15% to about 35% of the plasticizer, (c) from about 2% to about 25% of the thermoplastic po~ymeric resin, and (d) from about 3% to ~ -about 15% of the adhesion promotion system. A preferred composition consists essentially ~a) from about 23% to about 32% of the polyvinyl chloride resin, (b) from about lg% to about 30% of the plasticizer, (c) from about 5% to -about 20% of the thermoplastic polymeric resin, (d) from about 5% to about 13% of adhesion promoter, and (e) the balance selected from the group consisting of a wax, heat stabilizer, filler, pigment, wetting agent, and mixtures thereof.
A particularly preferred composition in terms of performance and cost considerations consists essentially ~ -of (a) from about 25% to about 30% of the polyvinyl chloride resin, (b) from about 22% to about 30% of a plasticizer, (c) from about 10% to about 15% of the :
20~
thermoplastic polymeric resin, (d) from about 5% to about 11% of adhesion promoter, (e) from about 15% to about 20%
of a filler, (f) from about 0% to about 8% wax, and (g) from about 1% to about 4% of a heat stabilizer The aforedescribed compositions of the invention are unique in their ability to act as a structural adhesive and a sealant in the assembly of automotive bodies. Thus, the compositions are used in the body area of the assembly to bond various steel components such as hoods and roof panels. Additionally, the compositions are used in the body shop area where certain components which demand greater structural bonds as obtained by welding require a sealant to smooth over the weld. The compositions are heated from about 90F to about 160F and applied in any convenient manner, such as pumping, troweling, flowing! brushing or spraying. The compositions are thermally stable so that they can be heated and drawn from by a pumping operation for prolonged periods. Upon cooling the compositions harden to a state with an initial degree of adhesion which is adequate for the intended purpose. This solidification occurs depite the plastisol nature of the compositions.
The assembled automotive body components or body shell is next prepared for painting. Typically this involves phosphate cleaning, washing, immersing the body shell in a primer bath, applying an electric charge to effect electrodeposition of the primer to the body shell, and removing the primed body shell from the bath. The compositions originally applied as adhesives and sealants 30~ rémain in tack. That is, they are not washed out onto adioining surface areas of the body shell.
Subsequent to the priming step, if one is used, and prior to an oven bake, the body shell is top coated with a paint and oven baked to a totally cured state by . .
- .
: ~ ' - .... . .. . .. . , ., , ~.; . . ;:, . .
2~
plastisol fusion of the sealer and also the top coat paint. The fusion temperature is well above the -aforementioned application temperature. The applied compositions of the invention are also able to withstand these operations without causing cosmetic-type problems such as discoloration, tackiness, cracking, etc. -It should be apparent the compositions of the invention enjoy all the qualities of previously used hot applied adhesive compositions and vinyl plastisol compositions, collectively. The synergistic nature of the composition components without adverse properties is very unexpected. An added benefit flowing from one composition having such qualities is reduced inventory in not having to stock two separate products as well as a consequent 15 reduced administrative burden. -The following examples illustrate the invention.
: ~ , , . ~ . ,., , ,, . ~; ............ , : :, -', ` ' ` ` :,: . ' : i , .. ..... .. . . . .
-15- 20102~ :
Example I
A preferred thermally stable hot applied plastisol composition has the following formulation:
% , .
Polyvinyl chloride dispersion resin (1) 19 .00 Polyvinyl chloride blending resin (2)8.00 Diisodecyl phthalate plasticizer 28.00 Epoxidized soybean oil plasticizer (3) 2.00 10 Vinyl acetate ethylene copolymer thermoplastic resin (4) 13.00 3-methacryloxypropyl trimethoxy silane adhesion promoter (5) 0.30 Elastomeric modified liquid epoxy resin (6) 2.00 15 Calcium organic thixotropic agent (7) 0.50 Methacrylate ester adhesion promoter (8) 4.~0 Calcium carbonate filler (9) 8.04 Hydrophobic fumed silica filler (10)8.00 Calcium oxide filler 2.00 20 Anionic surfactant wetting agent (11) 0.16 Modified polyamide hardening agent (12) : 3.0 Cumene hydroperoxide 0.08 Tri-basic lead sulfate heat stabilizer (13) 1.00 Hydroquinone monomethyl ether 0.02 25 Tetrahydrophthalic anhydride adhesion promoter 0.30 Carbon black pigment 0.05 Titanium dioxide pigment 0.05 100 . 00 ~13 A homopolymer available from Huls Corp. as Vestolit .
(2) A copolymer of vinyl chloride and dibutyl maleate available from The Goodyear Tire and Rubber Co. as Pliovic MC-85 (3) Available from the C.P. Hall Co. as PlastHall ESO
(4) A hot applied resin available from USI Chemicals Co.
as Vynathene EY80031 (5) Available from Dow Corning as Z-6030 Silane (6) Available from Wilmington Chemical Corp. as Heloxy 8005.
as Vynathene EY80031 (5) Available from Dow Corning as Z-6030 Silane (6) Available from Wilmington Chemical Corp. as Heloxy 8005.
(7) Available from Ashland Chemical Co. as Ircogel 903 (8) Available from Sartomer Co. as Chemlink 9010 (9) Available from H.M. Royal Inc. as Roy Cal L
(10) Available from Cabot Corp. as Cab-0-Sil TS-720 (11) Available from BYK Chemie USA as Byk-W 960 15 (12) Available from Ciba-Geigy Corp. as Hardener HY 940 (13) Available from Eagle Picher Co. as EPIstatic .. ..
The above composition was subjected to various tests to demonstrate its suitability for the intended use.
20 Initially the thermal stability of the composition at : -application temperature is determined. Samples of the current composition were held in an oven at 120F and 140F respectively and the viscosity of each tested over a period of time. Viscosities of the samples, as expressed in centipoises adjusted to 81.5F was as follows:
:' Hrs 120F 140F
Initial 2,963,800 2,963,800 1 2,740,500 6,252,400 30 7 2,801,400 -.
-17- ~ ~10~36 The above results show that the composition's viscosity remains substantially constant at 120F for at least seven hours. At 140F, however, the viscosity of the composition increases significantly over time. Thus, the composition is viscosity stable up to at least 120F.
Another set of tests was used to show that the composition of this example has a sufficiently low viscosity at a pre-gel temperature to be pumpable. The viscosities of a sample of the composition is measured at various temperatures and plotted. Readings from the plot are as set forth below:
Tem~erature (F)ViscositY (centipoises~
1,640,240 lS 80 1,250,480 990,640 787,640 100 519,680 110 373,520 120 292,320 The above results show the viscosity of the ~-composition decreases with temperature and is low enough to be readily pumped at an application temperature of 25about 120F. The application temperature is lower than the temperature at which gelation begins.
Example II
The formulation disclosed in Example I was tested for adhesive strength on three galvanized steel substrates under various exposure conditions. The numbers reported ' , " - ' : ~ ' ' ,, ' ' ' ~ , ' :';. -' `,. .'., ' ' . ', ' . ' ' " :
2ol~2~6 are the force to detach 1" x 4" metal coupons with a 1 in.2 bonded area pulled at 2"/minute. The specimens were heat cured for 20 minutes at 325F and had a bond thickness of 0.030". An average fading force from three replicates is reported. % CF refers to the % of cohesive failure for a given condition.
', '. . ...
Adhesive Testing Results . -ELECTRO ---Shear Overlaps HOT DIP GALVANEAL GALVANEAL -Initial 389 100% CF 448 100% CF 463 100% CF
3 wks humidity 451 80% CF 477 67% CF 412 72% CF
3 wks 158F 654 100% CF 756 100% CF 659 93% CF
250 hrs. salt spray 441 53% CF 550 57% CF 369 47% CF -Corrosion* 548 78% CF --- ---*Exposed to 30 cycles each of: 5 hours at 158F, 15 minutes 5% sodium chloride solution; 19.25 hours 100F/100% humidity.
Exam~le III
.
This example demonstrates the need for an adhesion promotion system in the composition. A set of partial compositions (i.e. containing polyvinyl chloride resin containing but without a thermoplastic polymeric resin) were made and then tested for short term and long term adhesion. The compositions are:
. ., ' ' ' ' ' ' ' ' " ' ' .: '" ' . ' ' ' " , . , ' ` . ' . ~
-19- 201{~
Parts bv Wei~ht Homopolymer dispersion resin 20.0 20.0 20.020.0 20.0 20.0 Copolymer blending resin 8.4 8.4 8.48.4 8.4 8.4 Calcium carbonate filler 39.8 39.8 39.839.~ 39.8 39.8 -DIDP plasticizer 20.0 20.3 24.720.3 23.2 20.1 t-butyl perbonzoate0.08 0.08 0.080.08 0.08 0.08 tribasic lead 1.1 1.1 1.1 1.1 1.1 1.1 10 trimethalopropane ~ .
trimethacrylate 4.7 - 4.7 4.7 4.7 4.7 methacrylate silane 0.3 0.3 - 0.3 0.3 0.3 :
tetrahydrophtahlic anhydride 0.3 0.3 0.3 - 0.3 0.3 15 elastomeric modified epoxy resin 2.1 2.1 2.1 2.1 2.1 modified polyamide 3.2 3.2 3.2 3.2 - 3.2 - .: .
Adhesion Initial 10 8.5 1 9.5 3.5 10 20 Adhesion 2 weeks at room :
temperature 10 4.0 1 10 1 4 :
Adhesion 4 weeks at room .; ~
temperature 10 9.0 2 10 1 10 -Adhesion results were obtained as qualitative pulling of 1/2" x 1/2" bends of adhesive baked on a hot dipped galvanized panel for 6 minutes at 350F. A rating of 10 was judged as best with 100% cohesive failure and a rating of 0 was judged as worst with total adhesive : 3Q failure coupled with little or no failing force. Separate adhesions were pulled for samples made fresh and then aged at room temperature for two and four weeks respectively.
:
- , . ,: .. . ., , . ~ . ., .. , . . : . .. - : .
20~3~
,, Exam~le IV :
The composition in Example I can be modified to improve the paintability of the formulation. The :' composition of a paintable material is as follows:
%
Polyvinyl chloride dispersion resin 19.00 Polyvinyl chloride blending resin 8.00 Diisodecyl phthalate plasticizer 8.00 Vinyl acetate ethylene copolymer th0rmoplastic resin 13.00 :.
3-methacryloxypropyl trimethoxy silane ;:
adhesion promoter 0.30 ~ :
Elastomeric modified liquid epoxy resin 2.00 ~ :
Methacrylate ester adhesion promoter4.50 ~ .
Precipiated calcium carbonate filler (14) 16.80 :: ~-Polyamino amide (15) 3.00 - ~
Calcium oxide filler 2.00 ~:.
Cumene hydroperoxide 0.08 Tri-basic lead sulfate heat stabilizer 1.00 20 Hydroquinone monomethyl ether 0.02 Cis - 1, 2, 3, 6 - tetrahydrophthalic anhydride 0.30 Polypropylene glycol dibenzoate plasticizer (16) 10.00 Trioctyl trimellitate plasticizer 10.00 Polyadipic acid ester plasticizer (17) 2.00 (14) AYailable from H.M. Royal as Hankuenka CC
(15) Available from Sherex Chemical Company as Euretek 580 (16) Available from Velsicol Chemical Corporation as Benzoflex 400 (17) Available from C.P. Hall as Plasthall P-670 .
. ~ . : :
, .. . ; . . ... . .. .
2Q il~23fi Modifications and variations of an obvious nature are possible without departing from the scope of the invention as defined in the appended claims.
What is claimed is:
: ~'',:'. ' .
The above composition was subjected to various tests to demonstrate its suitability for the intended use.
20 Initially the thermal stability of the composition at : -application temperature is determined. Samples of the current composition were held in an oven at 120F and 140F respectively and the viscosity of each tested over a period of time. Viscosities of the samples, as expressed in centipoises adjusted to 81.5F was as follows:
:' Hrs 120F 140F
Initial 2,963,800 2,963,800 1 2,740,500 6,252,400 30 7 2,801,400 -.
-17- ~ ~10~36 The above results show that the composition's viscosity remains substantially constant at 120F for at least seven hours. At 140F, however, the viscosity of the composition increases significantly over time. Thus, the composition is viscosity stable up to at least 120F.
Another set of tests was used to show that the composition of this example has a sufficiently low viscosity at a pre-gel temperature to be pumpable. The viscosities of a sample of the composition is measured at various temperatures and plotted. Readings from the plot are as set forth below:
Tem~erature (F)ViscositY (centipoises~
1,640,240 lS 80 1,250,480 990,640 787,640 100 519,680 110 373,520 120 292,320 The above results show the viscosity of the ~-composition decreases with temperature and is low enough to be readily pumped at an application temperature of 25about 120F. The application temperature is lower than the temperature at which gelation begins.
Example II
The formulation disclosed in Example I was tested for adhesive strength on three galvanized steel substrates under various exposure conditions. The numbers reported ' , " - ' : ~ ' ' ,, ' ' ' ~ , ' :';. -' `,. .'., ' ' . ', ' . ' ' " :
2ol~2~6 are the force to detach 1" x 4" metal coupons with a 1 in.2 bonded area pulled at 2"/minute. The specimens were heat cured for 20 minutes at 325F and had a bond thickness of 0.030". An average fading force from three replicates is reported. % CF refers to the % of cohesive failure for a given condition.
', '. . ...
Adhesive Testing Results . -ELECTRO ---Shear Overlaps HOT DIP GALVANEAL GALVANEAL -Initial 389 100% CF 448 100% CF 463 100% CF
3 wks humidity 451 80% CF 477 67% CF 412 72% CF
3 wks 158F 654 100% CF 756 100% CF 659 93% CF
250 hrs. salt spray 441 53% CF 550 57% CF 369 47% CF -Corrosion* 548 78% CF --- ---*Exposed to 30 cycles each of: 5 hours at 158F, 15 minutes 5% sodium chloride solution; 19.25 hours 100F/100% humidity.
Exam~le III
.
This example demonstrates the need for an adhesion promotion system in the composition. A set of partial compositions (i.e. containing polyvinyl chloride resin containing but without a thermoplastic polymeric resin) were made and then tested for short term and long term adhesion. The compositions are:
. ., ' ' ' ' ' ' ' ' " ' ' .: '" ' . ' ' ' " , . , ' ` . ' . ~
-19- 201{~
Parts bv Wei~ht Homopolymer dispersion resin 20.0 20.0 20.020.0 20.0 20.0 Copolymer blending resin 8.4 8.4 8.48.4 8.4 8.4 Calcium carbonate filler 39.8 39.8 39.839.~ 39.8 39.8 -DIDP plasticizer 20.0 20.3 24.720.3 23.2 20.1 t-butyl perbonzoate0.08 0.08 0.080.08 0.08 0.08 tribasic lead 1.1 1.1 1.1 1.1 1.1 1.1 10 trimethalopropane ~ .
trimethacrylate 4.7 - 4.7 4.7 4.7 4.7 methacrylate silane 0.3 0.3 - 0.3 0.3 0.3 :
tetrahydrophtahlic anhydride 0.3 0.3 0.3 - 0.3 0.3 15 elastomeric modified epoxy resin 2.1 2.1 2.1 2.1 2.1 modified polyamide 3.2 3.2 3.2 3.2 - 3.2 - .: .
Adhesion Initial 10 8.5 1 9.5 3.5 10 20 Adhesion 2 weeks at room :
temperature 10 4.0 1 10 1 4 :
Adhesion 4 weeks at room .; ~
temperature 10 9.0 2 10 1 10 -Adhesion results were obtained as qualitative pulling of 1/2" x 1/2" bends of adhesive baked on a hot dipped galvanized panel for 6 minutes at 350F. A rating of 10 was judged as best with 100% cohesive failure and a rating of 0 was judged as worst with total adhesive : 3Q failure coupled with little or no failing force. Separate adhesions were pulled for samples made fresh and then aged at room temperature for two and four weeks respectively.
:
- , . ,: .. . ., , . ~ . ., .. , . . : . .. - : .
20~3~
,, Exam~le IV :
The composition in Example I can be modified to improve the paintability of the formulation. The :' composition of a paintable material is as follows:
%
Polyvinyl chloride dispersion resin 19.00 Polyvinyl chloride blending resin 8.00 Diisodecyl phthalate plasticizer 8.00 Vinyl acetate ethylene copolymer th0rmoplastic resin 13.00 :.
3-methacryloxypropyl trimethoxy silane ;:
adhesion promoter 0.30 ~ :
Elastomeric modified liquid epoxy resin 2.00 ~ :
Methacrylate ester adhesion promoter4.50 ~ .
Precipiated calcium carbonate filler (14) 16.80 :: ~-Polyamino amide (15) 3.00 - ~
Calcium oxide filler 2.00 ~:.
Cumene hydroperoxide 0.08 Tri-basic lead sulfate heat stabilizer 1.00 20 Hydroquinone monomethyl ether 0.02 Cis - 1, 2, 3, 6 - tetrahydrophthalic anhydride 0.30 Polypropylene glycol dibenzoate plasticizer (16) 10.00 Trioctyl trimellitate plasticizer 10.00 Polyadipic acid ester plasticizer (17) 2.00 (14) AYailable from H.M. Royal as Hankuenka CC
(15) Available from Sherex Chemical Company as Euretek 580 (16) Available from Velsicol Chemical Corporation as Benzoflex 400 (17) Available from C.P. Hall as Plasthall P-670 .
. ~ . : :
, .. . ; . . ... . .. .
2Q il~23fi Modifications and variations of an obvious nature are possible without departing from the scope of the invention as defined in the appended claims.
What is claimed is:
: ~'',:'. ' .
Claims (18)
1. A hot applied thermally stable plastisol composition having adhesive and sealant qualities useful in the assembly of automobile bodies said composition comprising:
(a) from about 20% to about 35% of a finely divided polyvinyl chloride resin which is capable of being dispersed in a plasticizer;
(b) from about 15% to about 35% of a plasticizer;
(c) from about 2% to about 25% of a thermoplastic polymeric resin which is solid at room temperature and flowable at a temperature of application; and (d) from about 3% to about 15% of an adhesion promotion system.
(a) from about 20% to about 35% of a finely divided polyvinyl chloride resin which is capable of being dispersed in a plasticizer;
(b) from about 15% to about 35% of a plasticizer;
(c) from about 2% to about 25% of a thermoplastic polymeric resin which is solid at room temperature and flowable at a temperature of application; and (d) from about 3% to about 15% of an adhesion promotion system.
2. The composition of claim 1 wherein the polyvinyl chloride resin is selected from the group consisting of homopolymers of vinyl chloride, copolymers of vinyl chloride with vinylidene chloride, vinyl acetate, maleic ester or styrene, and mixtures thereof.
3. The composition of claim 2 wherein the plasticizer is selected from the group consisting of monomeric esters of phthalic, benzoic, succinic, adipic,sebacic, talic, lauric, azelaic, caprylic, hexanoic, phosphoric, oleic, glutaric, trimellitic, and stearic acids, N,N-dimethyl oleoamide, oleyl nitride, N-ethyl toluenesulfonamide, 2,2,4-trimethyl -1,3-pentanediol benzoate isobutyrate, polymeric esters of succinic, adipic, sebacic, talic, lauric, azelaic, caprylic, hexanoic, benzoic, phthalic, phosphoric, oleic, glutaric, trimellitic, and stearic acids, and mixtures thereof.
4. The composition of claim 3 wherein said thermoplastic polymeric resin is selected from the group consisting of polyethylene, polyamides, polyvinyl butyrals, polyvinyl acetate, cellulose derivatives, polyesters, polymethyl methacrylates and ethacrylates, polyvinyl ethers, polyurethanes, ethylene vinyl acetate, vinyl acetate ethylene, vinyl acetate, acrylonitrile, acrylonitrile butadiene copolymer, chlorinated ethylene vinyl acetate, poly epsilon cuprolactone, methyl methacrylate, polybutylene terephthalate and mixtures thereof.
5. The composition of claim 4 wherein said adhesion promotion system contains an unsaturated organosilane, a acrylic monomer and an unsaturated acid or anhydride monomer.
6. The composition of 5 wherein said adhesion promotion system further includes an epoxy or modified epoxy resin and a hardening agent for said epoxy or modified epoxy resin.
7. The composition of claim 6 wherein said hardening agent is selected from the group consisting of polyamides, diethylenetriamine, methane diamine, m-phenylene diamine, diaminodiphenyl sulfone, tris (dimethyl amino methyl) phenol, disyandiamide, BF3-monoethyl amine and nadicmethyl anhydride.
8. The composition of claim 5 wherein said unsaturated organosilane is selected from the group consisting of vinyl trichlorosilane, vinyl triethoxy silane, vinyl trimethoxy silane, vinyl-tris-.beta.-methoxy-ethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxy propyl-tris-2 (methoxy-ethoxy) silane and vinyl triacetoxy silane.
9. The composition of claim 8 wherein said unsaturated organosilane is 3-methacryloxypropyl trimethoxy silane, said acrylic monomer is trimethatopropane trimethacrylate and said unsaturated anhydride monomer is tetrahydrophthalic anhydride.
10. The composition of claim 1 wherein said polyvinyl chloride resin is selected from the group consisting of homopolymers of vinyl chloride, copolymers of vinyl chloride with vinylidene chloride, vinyl acetate, maleic acid ester, or styrene, and mixtures thereof, said plasticizer is selected from the group consisting of monomeric esters of phthalic, benzoic succinic, adipic, sebacic, talic, lauric, azelaic, caprylic, hexanoic, phosphoric, oleic, glutaric, trimellitic, stearic acids, polymeric esters of succinic, adipic, sebacic, talic, lauric, azelaic, caprylic, hexanoic, benzoic, phthalic, phosphoric, oleic, glutaric, trimellitic, and stearic acids, and mixtures thereof.
said thermoplastic polymeric resin is selected from the group consisting of polyethylene, polyamides, polyvinyl butyrals, polyvinyl acetate, cellulose derivatives, polyesters, polymethyl methacrylates and ethacrylates, polyvinyl ethers, polyurethanes, ethylene vinyl acetate, vinyl acetate ethylene, vinyl acetate, acrylonitrile, acrylonitrile butadiene copolymer, chlorinated ethylene vinyl acetate, poly epsilon cuprolactone, methyl methacrylate, polybutylene terephthalate and mixtures thereof, said adhesion promotion system contains an unsaturated organosilane, an acrylic monomer and an unsaturated acid or anhydride monomer, and said adhesion promotion system further includes an epoxy or modified epoxy resin and a hardening agent for said epoxy or modified epoxy resin.
said thermoplastic polymeric resin is selected from the group consisting of polyethylene, polyamides, polyvinyl butyrals, polyvinyl acetate, cellulose derivatives, polyesters, polymethyl methacrylates and ethacrylates, polyvinyl ethers, polyurethanes, ethylene vinyl acetate, vinyl acetate ethylene, vinyl acetate, acrylonitrile, acrylonitrile butadiene copolymer, chlorinated ethylene vinyl acetate, poly epsilon cuprolactone, methyl methacrylate, polybutylene terephthalate and mixtures thereof, said adhesion promotion system contains an unsaturated organosilane, an acrylic monomer and an unsaturated acid or anhydride monomer, and said adhesion promotion system further includes an epoxy or modified epoxy resin and a hardening agent for said epoxy or modified epoxy resin.
11. The composition of claim 1 wherein said polyvinyl chloride resin is a mixture of 50-100% of a homopolymer dispersion resin and 0-50% of a copolymer blending resin where the compolymer is comprised of vinyl chloride maleic ester, said plasticizer is diisodecyl phthalate, said thermoplastic polymeric resin is an vinyl acetate ethylene resin having a vinyl acetate content of 50-70%, and said adhesion promoter containing an unsaturated organosilane, an acrylic monomer and an unsaturated acid or anhydride monomer.
12. The composition of claim 11 consisting essentially of (a) from about 23% to about 32% of the polyvinyl chloride resin (b) from about 19% to about 30%
of the plasticizer, (c) from about 5% to about 20% of the thermoplastic polymeric resin, (d) from about 5% to about
of the plasticizer, (c) from about 5% to about 20% of the thermoplastic polymeric resin, (d) from about 5% to about
13% of the adhesion promoter, and (e) the balance selected from the group consisting of a filler, wax, heat stabilizer, pigment, wetting agent, and mixtures thereof.
13. The composition of claim 12 consisting essentially of (a) from about 25% to about 30% of the polyvinyl chloride resin, (b) from about 22% to about 30%
of the plasticizer, (c) from about 10% to about 15% of the thermoplastic polymeric resin, (d) from about 5% to about 11% of the adhesion promoter, (e) from about 15% to about 20% filler, (f) from about 0% to about 8% wax, and (g) from about 1% to about 4% heat stabilizer.
13. The composition of claim 12 consisting essentially of (a) from about 25% to about 30% of the polyvinyl chloride resin, (b) from about 22% to about 30%
of the plasticizer, (c) from about 10% to about 15% of the thermoplastic polymeric resin, (d) from about 5% to about 11% of the adhesion promoter, (e) from about 15% to about 20% filler, (f) from about 0% to about 8% wax, and (g) from about 1% to about 4% heat stabilizer.
14. A method of bonding and/or sealing joint areas in metal assemblies using a composition having both adhesive and sealant properties which can be hot applied and can withstand a washing step without affecting the cured composition, said composition being a thermally stable hot applied plastisol consisting essentially of (a) from about 20% to about 35% of a finely divided polyvinyl chloride resin, (b) from about 15% to about 35% of a plasticizer, (c) from about 2% to about 25% of thermoplastic polymeric resin and (d) from about 3% to about 15% of an adhesion promotion system.
15. The method of claim 14 comprising the steps of:
(a) hot applying the plastisol composition to joint areas of a metal assembly;
(b) cooling the applied composition sufficiently to achieve sufficient bonding;
(c) applying a paint composition to the metal assembly; and (d) baking the metal assembly to cure the plastisol composition and the paint composition.
(a) hot applying the plastisol composition to joint areas of a metal assembly;
(b) cooling the applied composition sufficiently to achieve sufficient bonding;
(c) applying a paint composition to the metal assembly; and (d) baking the metal assembly to cure the plastisol composition and the paint composition.
16. The method of claim 15 wherein said polyvinyl chloride resin is selected from the group consisting of homopolymers of vinyl chloride, copolymers of vinyl chloride with vinylidene chloride, vinyl acetate, maleic ester or styrene, and mixtures thereof, said plasticizer is selected from the group consisting of monomeric esters of phthalic, benzoic succinic, adipic, sebacic, talic, lauric, azelaic, caprylic, hexanoic, phosphoric, oleic, glutaric, trimellitic, stearic acids, polymeric esters of succinic, adipic, sebacic, talic, lauric, azelaic, caprylic, hexanoic, benoic, phthalic, phosphoric, oleic, glutaric, trimellitic, and stearic acids, and mixtures thereof, and said thermoplastic polymeric resin is selected from the group consisting of polyethylene, polyamides, polyvinyl butyrals, polyvinyl acetates, cellulose derivatives, polyesters, polymethyl methacrylates and ethacrylates, polyvinyl ethers, polyurethanes, ethylene vinyl acetate, vinyl acetate ethylene, vinyl acetate, acrylonitrile, acrylonitrile butadiene copolymer, chlorinated ethylene vinyl acetate, poly epsilon cuprolactone, methyl methacrylate, polybutylene terephthalate and mixtures thereof, said adhesion promotion system contains an unsaturated organosilane, an acrylic monomer and an unsaturated and or anhydride monomer, and said adhesion promotion system further includes an epoxy or modified epoxy resin and a hardening agent for said epoxy or modified epoxy resin.
17. The method of claim 15 wherein said polyvinyl chloride resin is a mixture of 50-100% of a homopolymer dispersion resin and 0-50% of a copolymer blending resin where the compolymer is comprised of vinyl chloride and maleic ester, said plasticizer is diisodecyl phthalate, said thermoplastic polymeric resin is an vinyl acetate resin having a vinyl acetate content of 50-70%, and said adhesion promoter containing an unsaturated organosilane, an acrylic monomer and an unsaturated acid or anhydride monomer.
18. The method of claim 17 wherein said composition comprises (a) from about 23% to about 32% of the polyvinyl chloride resin, (b) from about 19% to about 30% of the plasticizer, (c) from about 5% to about 20% of the thermoplastic polymeric resin, (d) from about 5% to 13% of the adhesion promoter, and (e) the balance selected from the group consisting of a filler, wax, heat stabilizer, pigment, wetting agent, and mixtures thereof.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2010236 CA2010236A1 (en) | 1990-02-16 | 1990-02-16 | Hot plastisol compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2010236 CA2010236A1 (en) | 1990-02-16 | 1990-02-16 | Hot plastisol compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2010236A1 true CA2010236A1 (en) | 1991-08-16 |
Family
ID=4144311
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2010236 Abandoned CA2010236A1 (en) | 1990-02-16 | 1990-02-16 | Hot plastisol compositions |
Country Status (1)
Country | Link |
---|---|
CA (1) | CA2010236A1 (en) |
-
1990
- 1990-02-16 CA CA 2010236 patent/CA2010236A1/en not_active Abandoned
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