CN101605850A - The composition of styrene resin of low surface gloss degree and with the sheet material and the composite product of the low surface gloss degree of its preparation - Google Patents
The composition of styrene resin of low surface gloss degree and with the sheet material and the composite product of the low surface gloss degree of its preparation Download PDFInfo
- Publication number
- CN101605850A CN101605850A CNA2008800041305A CN200880004130A CN101605850A CN 101605850 A CN101605850 A CN 101605850A CN A2008800041305 A CNA2008800041305 A CN A2008800041305A CN 200880004130 A CN200880004130 A CN 200880004130A CN 101605850 A CN101605850 A CN 101605850A
- Authority
- CN
- China
- Prior art keywords
- styrene
- composition
- low surface
- surface gloss
- resin
- 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.)
- Granted
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 221
- 229920005989 resin Polymers 0.000 title claims abstract description 187
- 239000011347 resin Substances 0.000 title claims abstract description 187
- 239000000203 mixture Substances 0.000 title claims abstract description 101
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 34
- 239000002131 composite material Substances 0.000 title claims description 15
- 239000006224 matting agent Substances 0.000 claims abstract description 52
- 229920001971 elastomer Polymers 0.000 claims abstract description 46
- 239000005060 rubber Substances 0.000 claims abstract description 41
- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims abstract description 40
- 150000003440 styrenes Chemical class 0.000 claims abstract description 36
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004902 Softening Agent Substances 0.000 claims abstract description 24
- 229920006132 styrene block copolymer Polymers 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000007334 copolymerization reaction Methods 0.000 claims description 21
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 19
- 229920005992 thermoplastic resin Polymers 0.000 claims description 18
- -1 2-ethylhexyl Chemical group 0.000 claims description 17
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 14
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 13
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 9
- 229920001897 terpolymer Polymers 0.000 claims description 9
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 8
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 claims description 4
- QZRFWQBUYGHLMU-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.N#CC=CC=CC1=CC=CC=C1 QZRFWQBUYGHLMU-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012764 mineral filler Substances 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- YPDXSCXISVYHOB-UHFFFAOYSA-N tris(7-methyloctyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCC(C)C)C(C(=O)OCCCCCCC(C)C)=C1 YPDXSCXISVYHOB-UHFFFAOYSA-N 0.000 claims description 4
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 claims description 4
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 claims description 3
- 125000005591 trimellitate group Chemical group 0.000 claims description 3
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004808 2-ethylhexylester Substances 0.000 claims description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 claims description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 claims description 2
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 238000006735 epoxidation reaction Methods 0.000 claims description 2
- 239000005357 flat glass Substances 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- AYBSOYWZTRUFMW-UHFFFAOYSA-N furan-2,5-dione;prop-2-enenitrile;styrene Chemical compound C=CC#N.O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 AYBSOYWZTRUFMW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- VNNBZUFJRRODHO-UHFFFAOYSA-N prop-2-enenitrile;prop-1-en-2-ylbenzene Chemical compound C=CC#N.CC(=C)C1=CC=CC=C1 VNNBZUFJRRODHO-UHFFFAOYSA-N 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 150000001261 hydroxy acids Chemical group 0.000 claims 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims 1
- 239000011120 plywood Substances 0.000 claims 1
- 230000035939 shock Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- 239000002932 luster Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 238000012662 bulk polymerization Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 7
- 150000008360 acrylonitriles Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- ACYXOHNDKRVKLH-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile prop-2-enoic acid Chemical group OC(=O)C=C.N#CC=CC=CC1=CC=CC=C1 ACYXOHNDKRVKLH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000287680 Garcinia dulcis Species 0.000 description 1
- 239000005064 Low cis polybutadiene Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- 230000001795 light effect Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- LGDNMDSHQLWPAK-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical compound COC(=O)C(C)=C.N#CC=CC=CC1=CC=CC=C1 LGDNMDSHQLWPAK-UHFFFAOYSA-N 0.000 description 1
- NYBDEQVBEYXMHK-UHFFFAOYSA-N methyl prop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical compound COC(=O)C=C.N#CC=CC=CC1=CC=CC=C1 NYBDEQVBEYXMHK-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- NWJZFGOFYNPABH-UHFFFAOYSA-N prop-1-ene;prop-2-enenitrile Chemical group CC=C.C=CC#N NWJZFGOFYNPABH-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011145 styrene acrylonitrile resin Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/72—Fillers; Inorganic pigments; Reinforcing additives
Abstract
The present invention relates to a kind of composition of styrene resin of low surface gloss degree.Composition of the present invention is composed of the following components: (A) base resin that comprises rubber-modified styrene resin of 80～99.9 weight %; (B) the syndiotactic polystyrene matting agent of 0.1～20 weight %.Said composition also comprises (C) gross weight based on the styrene resin of the low surface gloss degree of being made up of base resin (A) and matting agent (B), 0.1～20 weight % as the hydrogenated styrene block copolymers that comprises styrene block and divinyl rubber block of expanding material, and comprise the softening agent of (D) 0.1～30% weight % in addition.Composition of the present invention also has excellent weathering resistance and shock-resistance except the performance that possesses the low surface gloss degree, therefore, it can be applied in the multiple product, especially for the externally applied product of the buildings of for example wallboard and window frame etc.
Description
Technical field
The present invention relates to a kind of composition of styrene resin of low surface gloss degree, the sheet material that uses its preparation and composite product.More specifically, the present invention relates to a kind of composition of styrene resin of low surface gloss degree, the sheet material that uses its preparation and composite product, because the weathering resistance of said composition excellence and the surface gloss of shock strength and minimizing, it is particularly suitable for being used in the outside of buildings, for example, wallboard, window frame etc.
Background technology
The example that comprises the styrol copolymer of resin matrix and elastomerics or rubber is acrylate-styrene-acrylonitrile (ASA), alkene-styrene-acrylonitrile (OSA), vinyl cyanide-propylene diene rubber (EPDM)-vinylbenzene (AES) and acrylonitrile-butadiene-styrene (ABS) (ABS).These resins have different character according to its elastomeric component.Particularly, the ASA resin has excellent shock strength, workability and weathering resistance, and ABS resin has excellent low temperature shock-resistance and workability.
In the various fields that comprise household supplies, automotive interior material, office equipment and material of construction for the demand of the thermoplastic resin of for example ABS and ASA resin in continuous increase.90) or medium surface gloss (75 ° of glossiness: 60) the most of products that use these thermoplastic resin compositions to produce have high glossiness, and have high surface gloss (75 ° of glossiness: by the extruded product of ABS, AES and ASA resins.
Along with the requirement that recently the continuous increase of the susceptibility of beauty is produced for the emotion quality of product according to client, for the demand of the resin of low surface gloss degree also in continuous increase.In addition,, directly use the low-luster resin, eliminate simultaneously and use the step of low-luster paint and covering plate to become a kind of new trend for producing along with the pass to environment protection can't cut increase.Especially, for the production of building panel, computer housing and keyboard, electrical equipment and auto parts, the use of the resin combination of low surface gloss degree has significantly increased.Therefore, at building field, particularly produce certain preferred ABS, AES and ASA resin in the field of the buildings external application goods comprise wallboard, especially preferably have the surface gloss of minimizing but have the ASA resin of the excellent properties identical with conventional ASA resin.
In order to produce the resin of low surface gloss degree, prevailing method is the smoothness of regulating resin surface, make its greater than the visible range with the scatter incident light line, cause producing unglazed (glossless) effect.
Usually the method for attempting is the coating of carrying out embossing or coating low-luster on the surface of moulded product.But these methods need extra step, increased production cost, and the moulded product of being produced have relatively poor no light effect in its surface and has relatively poor workability.
Another kind of ordinary method is to add special rubber or elastomeric component to improve the quality.Particularly, this method illustrates with following three kinds of methods.First method is to improve the method for ABS resin by the large size rubber particles (it prepares with mass polymerization) that uses mean diameter to be at least 2 μ m.But, except shock strength and thermotolerance are relatively poor, the low-luster effect deficiency of Zhi Bei resin in this way.Second method is to add the method that mean diameter is at least the unglazed filler of 5 μ m in resin.But even Zhi Bei resin has excellent formability in this way, but it still has the problem of low-luster effect deficiency and the non-constant of shock strength.The third method is by prepare the method for ABS resin with the properties-correcting agent of vinyl unsaturated carboxylic acid (ethylene-unsaturated carboxylic acid) for example and the abs polymer grafting by the emulsion polymerization preparation, because Zhi Bei resin has excellent shock strength and conventional physicals and low-luster effect in this way, so this method is used widely recently.But this resin has limitation equally, because when being applied to weathering resistance resin (ASA), thermotolerance and weathering resistance have all reduced.
United States Patent (USP) the 5th, 081 has been described a kind of matting agent that is used for thermoplastic resin No. 193, and it comprises the graft copolymer that contains as the low-cis-polybutadiene of rubber components.United States Patent (USP) the 5th, 237 has been described a kind of method that reduces surface gloss No. 004, and it is to realize by the polymer particle that adds 2～15 μ m sizes in the thermoplastic polymer composition with core/shell structure.United States Patent (USP) the 5th, 475 has been described a kind of forming composition with matting No. 053, and it comprises impact-resistance modified thermoplastic resin and the matting agent of ABS for example or ASA.United States Patent (USP) the 4th, 652 has been described a kind of formed material with matting No. 614, and it is by using neutral and acid graftomer prepares as matrix.United States Patent (USP) the 4th, 169, the ABS compound of having described to have low surface gloss degree or unglazed coatings for No. 869.United States Patent (USP) the 4th, 668, a kind of graftomer with matting has been described for No. 767, it comprises: the heterocyclic nitrogen matrix in particulate rubber of 20～0.1 weight parts, mean diameter and high second-order transition temperature to 10 ℃ that it contains the rubber of 5～80 weight % altogether and has 0.05～20.0 μ m; The aromatic vinyl monomer of 40～99.8 weight parts; The single acid or the diacid that contain polymerizable double bond of 20～0.1 weight parts; And the vinyl cyanide of 0～40 weight part.
But the limitation of all these ordinary methods is that in the properties of the surface gloss, surface quality, production cost and the workability that satisfy required quality and for example weathering resistance, shock strength, minimizing, these ordinary methods have at least a defective.
Summary of the invention
Technical problem
An object of the present invention is, overcome the problems referred to above of prior art, provide to be applicable to for example composition of styrene resin of the low surface gloss degree of surface gloss buildings external application material, that have excellent weather resistance, shock-resistance and minimizing of wallboard and window frame.
Another object of the present invention provides the composition of styrene resin of the low surface gloss degree with improved workability and shock-resistance.
Another purpose of the present invention provides sheet material and the composite product composition of styrene resin production, that be applicable to the skin plate that has the low surface gloss degree of improved workability by use, and the method that is used to produce these sheet materials and composite product.
Technical scheme
Above-mentioned purpose of the present invention and other purpose can be realized by following embodiments of the present invention.
Below will describe the present invention in detail.
In order to realize purpose of the present invention, the invention provides a kind of composition of styrene resin of low surface gloss degree.The styrene resin of the low surface gloss degree that composition of the present invention comprises comprises: (A) 80～99.9 weight % contain the base resin of rubber-modified styrene polymer; (B) 0.1～20 weight % is as the syndiotactic polystyrene of matting agent.Composition of the present invention comprises in addition: (C) based on the gross weight of the styrene resin of the low surface gloss degree of forming by base resin (A) and matting agent (B), and the styrene block of 0.1～20 weight % and as the divinyl rubber block and the hydrogenated styrene block copolymers of expanding material.Described rubber-modified styrene polymer is by in the presence of rubber styrene monomer and selected unsaturated ethylene ene compound copolymerization being prepared.
Here, preferred base resin (A) comprises the nonrubber modified phenylethylene multipolymer for preparing by with styrene monomer and the copolymerization of unsaturated ethylene ene compound in addition.Especially, described nonrubber modified phenylethylene multipolymer is preferably the mixture of styrene-acrylonitrile copolymer and styrene-acrylonitrile-(methyl) acrylate copolymer.
Further preferably, the composition of styrene resin of low surface gloss degree of the present invention comprises in addition: (D) based on the gross weight of the styrene resin of the low surface gloss degree of forming by base resin (A) and matting agent (B), and the softening agent of 0.1～30 weight %.
75 ° of glossiness of the composition of styrene resin of low surface gloss degree of the present invention are 1～50.
The present invention also provides a kind of method of sheet material and sheet material of preparation in this way produced, and with forcing machine the composition of styrene resin of described low surface gloss degree is extruded in the temperature range of the temperature of low 20 ℃ of the fusing point from least 180 ℃ to specific extinction agent at least in described method.
The present invention provides a kind of at least one surface that covers internal layer that comprises to be exposed to the outer field composite product of outside atmosphere to prevent internal layer again.At this moment, described internal layer is with not having and the thermoplastic resin preparation of outer identical good weatherability properties, and skin to be composition of styrene resin with described low surface gloss degree prepare.
The inventor confirms, when with the weathering resistance styrene resin with as the syndiotactic polystyrene (sPS) of matting agent preparation composition, matting agent wherein can significantly reduce the glossiness of styrene resin and not destroy the weathering resistance and the shock-resistance of this styrene resin, finds that based on these inventor has finished the present invention.Therefore, the inventor has finished the present invention by confirming following content: comprise the weathering resistance styrene resin, as the syndiotactic polystyrene (sPS) of matting agent with for example improve the expanding material of workability and the thermoplastic resin composition of other additive of softening agent (wherein being adjusted in the rubber in the styrene resin and the content of matting agent) has excellent dropping hammer or dart impact strength, weathering resistance and low surface gloss degree effect.
The composition of styrene resin of low surface gloss degree of the present invention comprises: (A) 80～99.9 weight % contain the base resin of rubber-modified styrene polymer; (B) 0.1-20 weight % is as the syndiotactic polystyrene of matting agent.
The composition of styrene resin of low surface gloss degree of the present invention comprises: (A) 80～99.9 weight % contain the base resin of rubber-modified styrene polymer; (B) 0.1-20 weight % is as the syndiotactic polystyrene of matting agent, and comprise in addition: (C) based on the gross weight of the styrene resin of the low surface gloss degree that comprises base resin (A) and matting agent (B), the styrene block of 0.1～20 weight % and as the divinyl rubber block and the hydrogenated styrene block copolymers of expanding material.The composition of styrene resin of low surface gloss degree of the present invention comprises in addition: (D) based on the gross weight of the styrene resin of the low surface gloss degree of forming by base resin (A) and matting agent (B), and the softening agent of 0.1～30 weight %.
When measuring with TOYOSEIKI glossmeter (UD), 75 ° of glossiness of the composition of styrene resin of low surface gloss degree of the present invention are 1～50.
Below describe the component of the present composition in detail.
In this manual, for convenience's sake, (a) rubber-modified styrene polymer and (b) nonrubber modified phenylethylene multipolymer be referred to as (A) styrene resin, it will be base resin of the present invention.And (A) styrene resin and be called the styrene resin of low surface gloss degree as (B) syndiotactic polystyrene of matting agent together.
Therefore, the composition of styrene resin of low surface gloss degree of the present invention must comprise the styrene resin of low surface gloss degree, and comprises (C) expanding material and/or (D) softening agent in addition.
(A) styrene resin
The styrene resin that is used for the present composition refers to the copolymer resin for preparing by styrene monomer and other copolymerization of copolymerization monomer, and it comprises rubber-modified styrene monomer and nonrubber modified phenylethylene multipolymer by the copolymerization preparation of styrene monomer and unsaturated ethylene ene compound (unsaturated ethylene cmpound).Here, described unsaturated ethylene ene compound refers to the compound with carbon-to-carbon double bond and carbon-non-carbon unsaturated link(age).
The styrene monomer here not only comprises vinylbenzene but also comprises and contain substituent styrene derivatives.
(a) rubber-modified styrene polymer
Rubber-modified styrene polymer of the present invention is preferably by preparing styrene monomer and selected unsaturated ethylene ene compound copolymerization in the presence of elastomer rubber.
Described elastomer rubber can contain C by polymerization
1～C
32Alkyl, more preferably C
1～C
8The alkyl acrylate of alkyl, divinyl, isoprene, alkene and their mixture and prepare.At this moment, being used for preparing the comonomer of described rubber can be for being selected from one or more compounds of unsaturated ethylene ene compound, styrene monomer and multifunctional monomer.The content that is used to prepare the multipolymer of described rubber will reach the degree that can express rubber performance.The content accepted of these comonomers is known for those of skill in the art, and can regulate by experiment.
Described elastomer rubber can be selected from polyhutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile butadiene copolymer, alkyl acrylate rubber, ethylene-propylene rubber(EPR) (EPM), ethylene-propylene-elastoprene (EPDM) and the silicon rubber.
The preferred content of elastomer rubber is 5～50 weight % in rubber-modified styrene resin.The proper content of described rubber is very important for the present composition that production has satisfied shock-resistance.If rubber content is too high, then hardness and scuff resistance will reduce.Described styrene monomer can be selected from vinylbenzene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene, a vinyl toluene, 1, in 3-dimethyl styrene and the t-butyl styrene.In these monomers, optimization styrene, alpha-methyl styrene, p-methylstyrene or t-butyl styrene.And more preferably vinylbenzene or alpha-methyl styrene.
Rubber-modified styrene polymer can prepare by only copolymerization rubber and styrene monomer, but preferably, by copolymerization rubber, styrene monomer and unsaturated ethylene compound rubber-modified styrene polymer.
Described unsaturated ethylene ene compound can be selected from vinyl cyanide, methacrylonitrile, vinylformic acid C
1～C
4Alkyl ester and methacrylic acid C
1～C
4In alkyl ester, vinylformic acid, methacrylic acid, maleic anhydride and the acrylamide, and in these compounds, preferred vinyl cyanide.
Preferred content at the ene compound of unsaturated ethylene described in the rubber-modified styrene polymer is 5～50 weight %.Above-mentioned content helps improving thermotolerance, chemical resistant properties and physical strength.At this moment, the content of styrene monomer is 40～90 weight % in rubber-modified styrene polymer, more preferably 50～70 weight %.Described content range helps improving physical strength and shock strength.
The method that is used to produce rubber-modified styrene polymer is known for those of skill in the art, and the example is mass polymerization, solution polymerization, letex polymerization and suspension polymerization.Particularly be extensive use of letex polymerization.The rubber-modified styrene resin of Shi Yonging can be by any ordinary method preparation in the present invention.
(b) nonrubber modified phenylethylene multipolymer
For the rubber content of regulating styrene resin of the present invention or the physical properties (for example shock-resistance and weathering resistance) of regulating styrene resin of the present invention, described resin can comprise the nonrubber modified phenylethylene multipolymer by copolymerization of styrene monomer and unsaturated ethylene compound in addition except comprising rubber modified polymers.
Described unsaturated ethylene ene compound can be same as described above, and preferably the content in styrol copolymer is 20～80 weight %.
The styrol copolymer here can be for being selected from one or more compounds in the following multipolymer: styrene-acrylonitrile copolymer, styrene-acrylonitrile-methyl methacrylate copolymer, alpha-methyl styrene-acrylonitrile copolymer, styrene-methylmethacrylate copolymer, styrene-maleic anhydride copolymer, alpha-methyl styrene-styrene-acrylonitrile terpolymer, styrene-acrylonitrile-maleic anhydride terpolymer, styrene-acrylonitrile-acrylic terpolymer and alpha-methyl styrene-styrene-acrylonitrile terpolymer
Especially, optimization styrene-acrylonitrile copolymer, styrene-acrylonitrile-(methyl) acrylate terpolymer or their mixture.
(b1) styrene-acrylonitrile copolymer (SAN)
San copolymer can prepare with mass polymerization or emulsion polymerization.The styrene monomer that comprises in san copolymer can be selected from the above-claimed cpd, and can comprise additionally having multiple substituent styrene monomer.
Acrylonitrile monemer in san copolymer can be for being selected from one or more compounds in vinyl cyanide, methacrylonitrile and the ethyl acrylonitrile, in addition, can comprise and contain multiple substituent other acrylonitrile monemer and without limits.In this manual, acrylonitrile derivative also can be understood as monomer or the acrylonitrile monemer based on vinyl cyanide.
In styrene-acrylonitrile copolymer, the content of acrylonitrile monemer is preferably 10～50 weight %.If content is less than 10 weight %, then the chemical resistant properties of product will reduce.On the contrary, if content greater than 50 weight %, then viscosity will increase, and causes workability to reduce.
The weight-average molecular weight that contains the nonrubber modified phenylethylene multipolymer of styrene monomer and acrylonitrile monemer is preferably 50,000～250,000.If weight-average molecular weight is beyond above-mentioned scope, then the performance of physical properties and appearance will be relatively poor.
(b2) styrene-acrylonitrile-(methyl) acrylate copolymer (SAN-MMA)
The styrene-acrylonitrile of Shi Yonging-(methyl) acrylate copolymer is preferably the multipolymer that the acrylonitrile monemer of the styrene monomer of alkyl methacrylate derivative by copolymerization 40～80 weight % or acrylic acid alkyl ester derivative, 15～40 weight % and 3～20 weight % prepares in the present invention.The method that is used to prepare described multipolymer is not specifically limited, but preferred suspension polymerization or mass polymerization.Particularly consider production cost, more preferably continuous bulk polymerization.
When preparing described multipolymer, can increase the content of vinyl cyanide with mass polymerization.When at the described multipolymer of aqueous phase polymerization, for example with emulsion polymerization or suspension polymerization, for example the vinyl cyanide derivative of wetting ability vinyl cyanide and acrylonitrile content generate homopolymer pro rata, cause the color of resin yellowing.But when preparing described multipolymer with mass polymerization, even along with the increase of vinyl cyanide derivative content, also less generation homopolymer has reduced the danger of color yellowing.Therefore, because the content that can increase the vinyl cyanide derivative is to improve chemical resistant properties and shock-resistance, so mass polymerization is preferred.The preferred content of vinyl cyanide derivative is 3～20 weight %.If the content of vinyl cyanide derivative will reduce chemical resistant properties, scuff resistance and shock strength less than 3 weight %.If content is greater than 20 weight %, then the color relation of resin can yellowing.
Simultaneously, if the content of methacrylic acid or alkyl acrylate and styrene monomer exceeds above-mentioned scope, then the transparency will reduce.
The styrene monomer that is used for polymerizing styrene-vinyl cyanide-(methyl) acrylate copolymer and acrylonitrile monemer are with above-mentioned the same.The example of methacrylic acid or acrylic acid alkyl ester derivative is methyl methacrylate, Jia Jibingxisuanyizhi and lauryl methacrylate(LMA), and in these monomers, more preferably methyl methacrylate.
Nonrubber modified phenylethylene multipolymer (b) can be extruded to mix and mix with styrene resin by the routine of using single screw extrusion machine or twin screw extruder.More specifically, under greater than 200 ℃ temperature with the melt thorough mixing of rubber-modified styrene polymer (a) and nonrubber modified phenylethylene multipolymer (b).
Described styrene resin can comprise additive in addition, for example filler, compatible plastics, static inhibitor, antioxidant, fire retardant or lubricant.Based on 100 parts by weight of styrene resins, here the addition of additive can be 0.1～70 weight part.
Based on the styrene resin of 100 weight parts, styrene resin can comprise the pigment or the dyestuff of 0.02～10 weight part in addition.
Rubber-modified styrene polymer can be ASA, ABS or AES resin.Nonrubber modified phenylethylene multipolymer (b) can be for comprising (b1) styrene-acrylonitrile (SAN) multipolymer and (b2) resin of styrene-acrylonitrile-methyl methacrylate (SAN-MMA) terpolymer.Preferred ASA resin or the ASA resin of using uses with san copolymer and SAN-MMA multipolymer.
Particularly preferably be by mixing the styrene resin of following material preparation: by rubber-modified styrene resin (a) with vinylbenzene and vinyl cyanide (weight ratio=75: 25) grafted propylene acid butyl ester or the preparation of vinylformic acid tricyclodecenyl esters elastomer rubber; The styrene-acrylonitrile copolymer (b1) that contains the vinyl cyanide of 22～25 weight %; Styrene-acrylonitrile-methyl methacrylate copolymer (b2) with the methacrylic ester that comprises 60～80 weight %.
In the composition of styrene resin of the low surface gloss degree of 100 weight parts, the preferred content of described styrene resin (A) is 80～99.9 weight %.When content was in above-mentioned scope, physical strength was excellent and particularly improved weathering resistance and low-luster effect.
(B) matting agent
The matting agent that uses in the present invention is the syndiotactic polystyrene (sPS) as crystalline polymer.Here, syndiotactic polystyrene not only comprises the polystyrene by the preparation of polymerizing styrene monomer, and comprises the polystyrene copolymer by copolymerization of styrene monomer and comonomer preparation.Described styrene monomer comprises vinylbenzene, and comprises styrene derivatives.Being used for being up to 10 weight % with the add-on of the comonomer of styrene monomer copolymerization, more specifically is 0.1～10 weight %, and this comonomer is selected from maleic anhydride, toxilic acid, fumaric acid and the glycidyl methacrylate.Described syndiotactic polystyrene contains carboxylic acid at its at least one end.Therefore, described syndiotactic polystyrene (sPS) can be selected from syndiotactic polystyrene (sPS-COOH), maleic anhydride-syndiotactic polystyrene (sPS-MAH), toxilic acid-syndiotactic polystyrene (sPS-MA), fumaric acid-syndiotactic polystyrene (sPS-FA) and the glycidyl methacrylate-syndiotactic polystyrene (sPS-GMA) of polystyrene, carboxy blocking.
Matting agent sPS has the space structure of common known syndiotactic structure, a main chain that is formed by the C-C key is wherein arranged and comprise phenyl or the side chain of the phenyl of replacement is positioned on the main chain relative to one another.Different with the unbodied common random isotactic polystyrene of routine, described matting agent is a kind of polymkeric substance with crystalline structure.Its space structure can characterize by measuring tacticity with C13-NMR.
The sPS here comprises cinnamic multipolymer or copolymer mixture, for example have at least 85% tacticity under the situation of two tuples and under the situation of five-tuple (racemize five-tuple), having the polystyrene of at least 35% tacticity, poly-halogenated styrenes, poly-alkoxystyrene, polyoxyethylene alkylphenyl ethene, polyphenyl manthanoate vinylbenzene, or styrene derivatives is as main component.
The melt temperature of described matting agent is about 260～280 ℃.Compare with the conventional styrene polymer with atactic structure, this reagent has excellent thermotolerance and mechanical property.
In the low surface gloss degree composition of styrene resin of 100 weight parts, the preferred content of described matting agent is 0.1～20 weight %, more preferably 1～10 weight %.When content was in above-mentioned scope, shock strength was excellent and improved no light property.
(C) expanding material
In the present invention, using expanding material is in order to increase the miscibility of syndiotactic polystyrene (sPS) and styrene resin.The expanding material here can be for containing the styrene block copolymer that vinylbenzene repeats block and divinyl rubber block, and hydrogenated styrene block copolymers more preferably.The divinyl rubber block can perhaps prepare by the comonomer copolymerization with divinyl or butadiene derivatives and for example ethene and propylene by polymerization divinyl or for example butadiene derivatives preparation of isoprene.The preferred example of styrene block copolymer is the styrene block copolymer (SEBS) by the structure with styrene block-divinyl rubber block-styrene block of the copolymerization preparation of divinyl rubber block and ethene.
Styrene block copolymer in the present invention is preferably hydrogenated styrene block copolymers.The hydrogenation of divinyl rubber block can improve weathering resistance.In styrene block copolymer, can form one or more blocks by styrene block with as the polymerization of the maleic anhydride of comonomer.In block, add maleic anhydride and can improve thermotolerance.The preferred content of comonomer in block (particularly maleic anhydride) is about the highest 10 weight %, particularly is 0.1～10 weight %.The example of expanding material of the present invention is the maleic anhydride-hydrogenated styrene/butadiene/styrene copolymers (SEBS-MAH) that contains the maleic anhydride of the 1.5 weight % that have an appointment.This hydrogenated styrene block copolymers is on sale on market, and its preparation method also is known.
In the styrene resin of the low surface gloss degree of being made up of base resin (A) and matting agent (B), the preferred content of expanding material of the present invention is 0.1～20 weight %, is preferably 0.5～10 weight %.If content is lower than 0.1 weight %, then miscibility will be poor.On the contrary, if content greater than 10 weight %, particularly greater than 20 weight %, will increase production cost.
(D) be used to improve the additive of workability
In the present invention, as the additive that improves workability, can use softening agent.At this moment, can use the softening agent of any routine, for example based on the softening agent of phthalic ester, such as dibutyl phthalate (DBP), phthalic acid two (2-ethylhexyl) ester (DEHP or DOP), diisononyl phthalate (DINP), Di Iso Decyl Phthalate (DIDP) and butyl benzyl phthalate (BBP); Based on the softening agent of trimellitate, such as tri trimellitate (ethylhexyl) ester (TEHTM or TOTM), triisononyl trimellitate (TINTM) and triisodecyl trimellitate (TIDTM); Based on the softening agent of phosphoric acid ester, such as Tritolyl Phosphate (TCP), tri-2-ethylhexyl phosphate (TEHP or TOP), tricresyl phosphate biphenyl ester (CDP) and triaryl phosphate (TAP); Based on the softening agent of epoxy, such as epoxidised soybean oil (ESO) and epoxidation linseed oil ((ELO); Based on the softening agent of polyester, such as molecular-weight average 1,000～8,000 oligomeric polyester; Based on the softening agent of lipid acid, such as hexanodioic acid two (2-ethylhexyl) ester (DEHA or DOA), nonane diacid two (2-ethylhexyl) ester (DOZ) and diisodecyl adipate (DIDA); And based on the softening agent of clorafin.
In the present invention, the fusing point of described syndiotactic polystyrene resin (sPS) is about 270 ℃.When this resin was mixed with styrene resin, melt viscosity reduced and has reduced thus workability.Therefore, in order to improve the workability of composition of the present invention, use softening agent to improve workability as additive.Especially, Di Iso Decyl Phthalate (DIDP) is most preferred softening agent.In the low surface gloss degree styrene resin of being made up of base resin (A) and matting agent (B), the preferred content of softening agent is 0.1～30 weight %, more preferably 0.5～15 weight %.If content is lower than 0.1 weight %, then miscibility will be poor.On the contrary, if content greater than 15 weight %, particularly greater than 30 weight %, will increase production cost.
The composition of styrene resin of low surface gloss degree of the present invention can be by using single screw rod or twin screw extruder by each component being mixed and extruding with produced in particle form.At this moment, in order to mix and extrusion compositions, the tube temperature of forcing machine must be able to not be significantly less than the fusing point as the syndiotactic polystyrene of matting agent.But, still preferably extrude at low temperatures to prevent the rubber-modified styrene polymer deterioration.Usually, more than the fusing point of syndiotactic polystyrene, extrude, but preferably extrude, but difference is not more than 10 ℃ at this moment, and more preferably difference is not more than 20 ℃ in the temperature of the fusing point that is lower than syndiotactic polystyrene.
When measuring with TOYOSEIKI glossmeter (UD), 75 ° of glossiness of the composition of styrene resin of low surface gloss degree of the present invention are 1～50, preferred 15～35.
The composition of styrene resin of described low surface gloss degree can comprise unglazed filler in addition.When unglazed filler uses with matting agent, significantly reduced glossiness, make and further improved low surface gloss degree effect and the reduction of mechanical property is minimized.As unglazed filler, B-Mat (crosslinked SAN, second-order transition temperature: 122 ℃) and mineral filler are known.Described mineral filler can be for being selected from one or more compounds in spherical or the flaky inorganic filler, for example based on mineral filler (for example: talcum, mica, clay, montmorillonite and granulated glass sphere), silicon-dioxide, sheet glass, lime carbonate and the metal oxide of silicate.The unglazed filler here can be cross-linked styrene-acrylonitrile copolymer.
The present invention also provides by the sheet material of the composition of styrene resin preparation of described low surface gloss degree and the composite product of being made up of above-mentioned sheet material and other thermoplastic resin sheet material, and the method for preparing them.
The sheet material here can prepare by the composition of styrene resin that uses single screw rod or twin screw extruder to extrude particulate state low surface gloss degree.At this moment, processing temperature is at least 180 ℃, and preferably than low at least 20 ℃ of the fusing point of described matting agent.When processing temperature satisfies above-mentioned condition, can show gloss character preferably.
Above-mentioned extrusion temperature also is applicable to by coextrusion and prepares composite product by the sheet material of the composition of styrene resin preparation of low surface gloss degree of the present invention and one or more other thermoplastic resin sheet materials that are selected from acrylonitrile-butadiene-styrene resin and the polyvinyl chloride (PVC) RESINS.At this moment, extrusion temperature is preferably the temperature about described thermoplastic resin fusing point, more accurately is about 200 ℃ (they are the fusing point that is used for the polyvinyl chloride of vinylchloride resin plate material coextrusion).Described thermoplastic resin can contain impact modifier, processing aid, thermo-stabilizer, antioxidant, UV stablizer, filler, lubricant or pigment.
The present invention also provides a kind of at least one surface that comprises internal layer and covering internal layer to be exposed to the outer field composite product of outside atmosphere to prevent internal layer.At this moment, described internal layer is with not having and the thermoplastic resin preparation of outer identical good weatherability properties, and skin to be composition of styrene resin with described low surface gloss degree prepare.The thermoplastic resin that constitutes internal layer can be for being selected from one or more thermoplastic resins in acrylonitrile-butadiene-styrene resin and the polyvinyl chloride (PVC) RESINS.Described thermoplastic resin can contain impact modifier, processing aid, thermo-stabilizer, antioxidant, UV stablizer, filler, lubricant or pigment.
In this composite product, internal layer can be individual layer or multilayer.Outer can being laminated on the two sides of internal layer.Illustrated as mentioned, can internal layer and skin be combined continuously by the coextrusion of using forcing machine.Skin has excellent weathering resistance, so it can protect internal layer to avoid the influence of ray and weather.Therefore, composite product of the present invention can be used as in the externally applied product of buildings, for example wallboard and window frame.
Description of drawings
Can understand the application of preferred implementation of the present invention with reference to the accompanying drawings best.
Fig. 1 illustrates and comprises SAN-MMA by use and have than comprising as the resin of the inventive method of the styrene resin of base resin preparation and do not comprise the resin better weather resistance of SAN-MMA as the styrene resin of base resin.
Fig. 2 illustrates at the composition that contains softening agent and does not contain between the composition of softening agent correlated apparent viscosity with the variation of apparent shear rate.
Embodiment
Shown in the following examples, for example understand the present invention feasible and preferred embodiment at present.
But, should be appreciated that according to present disclosure those of skill in the art can improve and improve within the spirit and scope of the present invention.
[embodiment]
Embodiment 1～4, comparing embodiment 1
According to rubber content, contain the SA927-DP resin (LG Chemical Ltd., Korea S) of acrylic rubber and SAN resin (SAN 90HR, LG Chemical Ltd., Korea S) that MI is 25g/10min (220 ℃) preparation styrene resin by mixing.
As matting agent, and use sPS 130ZC (fusing point: 270 ℃, bright dipping Industry Co., Ltd (IdemitsuKosan Co., Ltd.), Japan).
According to styrene resin and matting agent being joined in the forcing machine that disposes 27mm twin screw (Leistriz, Germany), to wherein adding 3 parts by weight of titanium oxide (Cronos2233) at the composition shown in the table 3.Under the processing conditions shown in the table 1, preparing particle after the mixing.
Under the condition shown in the table 2, use described granules preparation sheet material (thickness 0.2mm) by TSE16TC twin screw extruder (screw diameter: 16mm, Thermo PRISM) and T type mouth mould.Measure 75 ° of glossiness with TOYOSEIKI glossmeter (UD), the results are shown in table 3.In order to show the no optical property of the sheet material of extruding in the T type mouth mould, processing is carried out under the temperature of low 20 ℃ of the fusing point of specific extinction agent.
Table 1
| Forcing machine | Tube 1 | |
The mouth mould | Screw rod RPM | Injection rate |
| ?Leistritz | ??250℃ | ?260℃ | ??260℃ | ?350 | ??15kg/hr |
Table 2
| Forcing machine | Tube 1 | |
The mouth mould | Screw rod RPM | Injection rate |
| ??Thermo | ??190℃ | ??200℃ | ??200℃ | ?250 | ??3kg/hr |
Table 3
| Embodiment 1 | |
Embodiment 3 | |
Comparing embodiment 1 | |
| Styrene resin (weight %) | ??97 | ??95 | ??93 | ??90 | ??100 |
| Matting agent (weight %) | ??3 | ??5 | ??7 | ??10 | ??0 |
| Glossiness (75 °) | ??32.5 | ??17.5 | ??9.3 | ??3.3 | ??84.9 |
As shown in table 3, comprise sPS and have the low glossiness of resin combination than the comparing embodiment 1 that does not contain matting agent as the composition of styrene resin of the embodiment 1～4 of matting agent, show that composition of the present invention has excellent low surface gloss degree character.
Embodiment 5～7
Contain the MAH of 1.5 weight % and to have 269 ℃ the sPS-MAH TPSPS 8012PA (KOMETRA) of fusing point except using as the matting agent according to the composition shown in the table 4, with embodiment 1 in the same way as described experimentize.
Table 4
| Embodiment 5 | |
Embodiment 7 | |
| Styrene resin (weight %) | ??97 | ??95 | ??90 |
| Matting agent (weight %) | ??3 | ??5 | ??10 |
| Glossiness (75 °) | ??45.8 | ??25.9 | ??3.6 |
As shown in table 4, comprise sPS-MAH and have the low glossiness of resin combination, show that composition of the present invention has excellent low surface gloss degree character than the comparing embodiment 1 that does not contain matting agent as the composition of styrene resin of the embodiment 5～7 of matting agent.
Except the Blendex-MAT that uses 3 and 5 weight parts respectively as the unglazed filler, with embodiment 1 in the same way as described experimentize.
Table 5
| |
Embodiment 9 | |
| Styrene resin (weight %) | ??97 | ??97 |
| Matting agent (weight %) | ??3 | ??3 |
| Blendex-MAT (weight part) | ??3 | ??5 |
| Glossiness (75 °) | ??29.4 | ??23.3 |
As shown in table 5, the composition of styrene resin that also contains the embodiment 8～9 of unglazed filler except matting agent sPS has the glossiness lower than the resin combination of embodiment 1, shows that these compositions have better low surface gloss degree character.
For glossiness in the production process of observing the styrene resin in embodiment 1 with the variation of processing temperature, the sPS-MAH TPSPS 8012PA (KOMETRA) of 10 weight % is joined in the styrene resin of 90 weight % as matting agent.Except control processing temperature as shown in table 6, with embodiment 1 in the same way as described experimentize.
[table 6]
As shown in table 6, the composition of the comparing embodiment 2 of processing under the composition of styrene resin of the embodiment 10～19 that processes under the temperature of low at least 20 ℃ of the fusing point of specific extinction agent and the temperature that is exceeding above-mentioned scope in the sheet material preparation process is compared, and shows excellent no optical property.
Embodiment 20～22, comparing embodiment 3 and 4
(A) according to the weight ratio shown in the table 2, by mixing SA927-DP resin (LG Chemical Ltd. that (a) contains acrylic rubber, Korea S) and (b1) MI is SAN resin (SAN 90HR, LG Chemical Ltd., Korea S) the preparation styrene resin of 25g/10min (220 ℃).(B) as matting agent, and use sPS 130ZC (fusing point: 270 ℃, bright dipping Industry Co., Ltd (IdemitsuKosan Co., Ltd.), Japan).(C), use SEBS-MAH Scona TPKD8112 (Kometra) as expanding material.
According in (the unit: weight part) styrene resin, matting agent and expanding material are joined in the forcing machine, of the composition shown in the table 9 to wherein adding 0.5 parts by weight of titanium oxide (Cronos 2233).Under the processing conditions shown in the table 7, using twin screw (diameter: 27mm, Leistritz, Germany) forcing machine to prepare particle after the mixing.
Under the condition shown in the table 8, use described granules preparation sheet material (thickness 3mm) by TSE16TC 3-layer extruding (EM, Korea S) and T type mouth mould.Measure 75 ° of glossiness with TOYOSEIKI glossmeter (UD), the results are shown in table 3.In order to show the no optical property of the sheet material of extruding in the T type mouth mould, processing is carried out under the temperature of low 20 ℃ of the fusing point of specific extinction agent.
The following evaluation of carrying out physical properties.
(1) glossiness: TOYOSEIKI (glossmeter UD) measures (%) for 75 °
(2) shock strength: ASTM D-256 (kg.cm/cm)
(3) weathering resistance: Atlas UV-2000
Condition-light source: UV-A lamp
-the stage 1 (UV)
-blackboard temperature: 60 ℃
-irradiance: 0.77W/m
2
When before atmospheric exposure test and the digital average value of Hunter Lab value afterwards near 0 the time, weathering resistance is good more.
(4) capillary test: RHEO-TESTER 1501 (temperature: 200 ℃, shearing rate: 1-3000s
-1)
Table 7
| Forcing machine | Tube 1 | |
The mouth mould | Screw rod RPM | Injection rate |
| ?Leistritz | ??260℃ | ??270℃ | ??270℃ | ??250 | ??15kg/hr |
Table 8
| Forcing machine | Tube 1 | |
The mouth mould | Screw rod RPM | Injection rate |
| EM, Korea S | ?190℃ | ??200℃ | ??200℃ | ??250 | ??3kg/hr |
Table 9
As shown in table 9, comprise sPS and have the low glossiness of resin combination than the comparing embodiment 3 that does not contain matting agent as the composition of styrene resin of the embodiment 20～22 of matting agent, show that these compositions have better low surface gloss degree character.As shown in embodiment 21 and the comparing embodiment 4, add expanding material and improved miscibility between styrene resin and the matting agent, cause the raising of shock strength.
Embodiment 23～26
Except basis is used XT500 (LG Chemical Ltd. at the composition shown in the table 10, Korea S) conduct has (b2) SAN-MMA resin and use DIDP (LG Chemical Ltd. of the MI of 50g/10min (220 ℃), Korea S) as softening agent improving beyond the workability, with experimentize in the same way as described in the embodiment 20.
Table 10
As shown in table 10, the composition of styrene resin of embodiment 23～26 shows and does not contain the resin combination the same good low-luster character of SAN-MMA with the comparing embodiment 5 of the additive that is used to improve workability.Particularly, embodiment 25 and 26 composition are used to improve the additive of workability by adding, and DIDP shows the shock-resistance of raising.
As shown in Figure 1, along with the increase of SAN-MMA content, DE changes less, and has improved weathering resistance thus.
As shown in Figure 2, add the reduction that the additive be used to improve workability causes melt viscosity, in fact this help producing.
Industrial applicibility
According to the present invention, by the base resin and the matting agent that will have excellent weather resistance and shock-resistance, syndiotactic polystyrene, the composition of styrene resin of the low surface gloss degree that is mixed with have kept the excellent weather resistance of the base resin that comprised and shock-resistance and have not had deterioration.In addition, in composition of the present invention, add expanding material and improved shock-resistance.
According to the present invention, in the composition of forming by base resin and matting agent, add the increase that softening agent causes workability and shock-resistance.
According to the present invention, in base resin, add the increase that the mixture that comprises rubber-modified styrene polymer and nonrubber modified phenylethylene multipolymer (particularly styrene-acrylonitrile copolymer and styrene-acrylonitrile-(methyl) acrylate copolymer) causes weathering resistance.
According to the present invention, under than the low temperature of the melt temperature of the syndiotactic polystyrene that is used as matting agent, composition of styrene resin by low surface gloss degree of the present invention has prepared sheet material, can improve the physicals of this sheet material by it, particularly weathering resistance and shock-resistance, and do not have deterioration.
Therefore, except the low-luster character of excellence, the sheet material and the composite product that prepare by the composition of styrene resin that uses the low surface gloss degree also have excellent weathering resistance and shock-resistance, they can be used in the multiple field thus, particularly comprise in the externally applied product of buildings of wallboard and window frame.
Those of skill in the art will understand, in aforementioned description disclosed imagination and embodiment can be easily with making improvements or design the basis that other is used to implement the embodiment of the identical purpose of the present invention.Those of skill in the art also will understand, and these embodiments that are equal to do not depart from the spirit and scope of the invention illustrated in appended claims.
Claims (29)
1, a kind of composition of styrene resin of low surface gloss degree, it comprises:
(A) base resin that comprises rubber-modified styrene polymer of 80～99.9 weight %; With
(B) 0.1～20 weight % is as the syndiotactic polystyrene of matting agent.
2, the composition of styrene resin of low surface gloss degree according to claim 1, wherein, described rubber-modified styrene polymer is by preparing styrene monomer and the copolymerization of nonessential unsaturated ethylene ene compound in the presence of rubber.
3, the composition of styrene resin of low surface gloss degree according to claim 2, wherein, described rubber is to be selected from polyhutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile butadiene copolymer, alkyl acrylate rubber, ethylene-propylene rubber(EPR), ethylene-propylene-elastoprene and the silicon rubber one or more.
4, the composition of styrene resin of low surface gloss degree according to claim 2, wherein, the content of rubber is 5～30 weight % in the described rubber-modified styrene polymer.
5, the composition of styrene resin of low surface gloss degree according to claim 2, wherein, described styrene monomer is selected from vinylbenzene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene, a vinyl toluene, 1, in 3-dimethyl styrene and the t-butyl styrene.
6, the composition of styrene resin of low surface gloss degree according to claim 2, wherein, described unsaturated ethylene ene compound is to be selected from the following compounds one or more: vinyl cyanide, methacrylonitrile, vinylformic acid C
1～C
4Alkyl ester and methacrylic acid C
1～C
4Alkyl ester, vinylformic acid, methacrylic acid, maleic anhydride, acrylamide and vinyl methyl ether.
7, the composition of styrene resin of low surface gloss degree according to claim 2, wherein, the content of rubber is 5～30 weight % in the described rubber-modified styrene polymer, and the content of styrene monomer is that the content of 40～90 weight % and unsaturated ethylene ene compound is 5～30 weight %.
8, the composition of styrene resin of low surface gloss degree according to claim 1, wherein, described base resin (A) comprises the nonrubber modified phenylethylene multipolymer by the copolymerization preparation of styrene monomer and unsaturated ethylene ene compound in addition.
9, the composition of styrene resin of low surface gloss degree according to claim 8, wherein, the content of unsaturated ethylene ene compound is 20～80 weight % in the described nonrubber modified phenylethylene multipolymer.
10, the composition of styrene resin of low surface gloss degree according to claim 8, wherein, described nonrubber modified phenylethylene multipolymer is to be selected from the following multipolymer one or more: styrene-acrylonitrile copolymer, styrene-acrylonitrile-methyl methacrylate copolymer, alpha-methyl styrene-acrylonitrile copolymer, styrene-methylmethacrylate copolymer, styrene-maleic anhydride copolymer, alpha-methyl styrene-styrene-acrylonitrile terpolymer, styrene-acrylonitrile-maleic anhydride terpolymer, styrene-acrylonitrile-acrylic terpolymer and alpha-methyl styrene-styrene-acrylonitrile terpolymer.
11, the composition of styrene resin of low surface gloss degree according to claim 8, wherein, described nonrubber modified phenylethylene multipolymer is the mixture of styrene-acrylonitrile copolymer and styrene-acrylonitrile-(methyl) acrylate copolymer.
12, the composition of styrene resin of low surface gloss degree according to claim 11, wherein, described styrene-acrylonitrile copolymer is the copolymerization preparation by the acrylonitrile copolymer of the styrol copolymer of 50～90 weight % and 10～50 weight %, and it has 50,000～250,000 weight-average molecular weight, and styrene monomer and the copolymerization preparation of the acrylonitrile monemer of 3～20 weight %s of described styrene-acrylonitrile-(methyl) acrylate copolymer by 40～90 weight % (methyl) acrylate monomers, 15～40 weight %.
13, the composition of styrene resin of low surface gloss degree according to claim 1, wherein, described syndiotactic polystyrene has at least 85% tacticity and have at least 35% tacticity under the situation of five-tuple (racemize five-tuple) under the situation of two tuples.
14, the composition of styrene resin of low surface gloss degree according to claim 1, wherein, described syndiotactic polystyrene contains hydroxy-acid group at its at least one end, or the copolymerization preparation by being selected from comonomer in maleic anhydride, toxilic acid, fumaric acid and the glycidyl methacrylate and styrene monomer, and the content of described comonomer is 0.1～10 weight %.
15, the composition of styrene resin of low surface gloss degree according to claim 1, wherein, described composition comprises in addition: (C) based on the gross weight of the styrene resin of the low surface gloss degree of being made up of base resin (A) and matting agent (B), 0.1～20 weight % is as the hydrogenated styrene block copolymers that comprises styrene block and divinyl rubber block of expanding material.
16, the composition of styrene resin of low surface gloss degree according to claim 15, wherein, described hydrogenated styrene block copolymers has the structure of styrene block-divinyl rubber block-styrene block, and the divinyl rubber block here is the diblock rubber by the copolymerization preparation of divinyl and ethene.
17, the composition of styrene resin of low surface gloss degree according to claim 15, wherein, at least one block of described hydrogenated styrene block copolymers is that the copolymerization by monomer in the block and maleic anhydride forms, and is 0.1～10 weight % of this block weight as the content of the maleic anhydride of comonomer.
18, the composition of styrene resin of low surface gloss degree according to claim 1, wherein, described composition comprises in addition: (D) based on the gross weight of the styrene resin of the low surface gloss degree of forming by base resin (A) and matting agent (B), and the softening agent of 0.1～30 weight %.
19, the composition of styrene resin of low surface gloss degree according to claim 18, wherein, described softening agent is to be selected from the following compounds one or more: dibutyl phthalate (DBP), phthalic acid two (2-ethylhexyl) ester (DEHP or DOP), diisononyl phthalate (DINP), Di Iso Decyl Phthalate (DIDP) and butyl benzyl phthalate (BBP); Tri trimellitate (ethylhexyl) ester (TEHTM or TOTM), triisononyl trimellitate (TINTM) and triisodecyl trimellitate (TIDTM); Tritolyl Phosphate (TCP), tri-2-ethylhexyl phosphate (TEHP or TOP), tricresyl phosphate biphenyl ester (CDP) and triaryl phosphate (TAP); Epoxidised soybean oil (ESO) and epoxidation linseed oil ((ELO); Molecular-weight average is 1,000～8,000 oligomeric polyester; Hexanodioic acid two (2-ethylhexyl) ester (DEHA or DOA), nonane diacid two (2-ethylhexyl) ester (DOZ) and diisodecyl adipate (DIDA); And based on the softening agent of clorafin.
20, the composition of styrene resin of low surface gloss degree according to claim 1, wherein, described composition comprises in addition: based on the gross weight of the styrene resin of the low surface gloss degree of being made up of base resin (A) and matting agent (B), the unglazed filler of 0.1～20 weight %.
21, the composition of styrene resin of low surface gloss degree according to claim 20, wherein, described unglazed filler is selected from crosslinked SAN, the mineral filler based on silicate, granulated glass sphere, silicon-dioxide, sheet glass, lime carbonate and the metal oxide.
22, the composition of styrene resin of low surface gloss degree according to claim 20, wherein, described unglazed filler is cross-linked styrene-acrylonitrile copolymer.
23, the composition of styrene resin of low surface gloss degree according to claim 1, wherein, the glossiness of described composition is 1～50 at 75 °.
24, by the sheet material of any one preparation in the composition of styrene resin of the low surface gloss degree described in the claim 1～23.
25, a kind of method of producing sheet material, it comprises the steps: by using forcing machine, at least 80 ℃ with hang down a kind of in the composition of styrene resin of extruding the low surface gloss degree described in the claim 1～23 under 20 ℃ the temperature at least than the fusing point of syndiotactic polystyrene matting agent.
26, the method for production sheet material according to claim 25, wherein, the sheet material of complex form prepares as follows: the composition of styrene resin of coextrusion thermoplastic resin composition and low surface gloss degree is to prepare two plates; With the extruding these two plates with the preparation multi-ply wood.
27, the method for production sheet material according to claim 26, wherein, described thermoplastic resin is one or more resins that are selected from acrylonitrile-butadiene-styrene resin and the polyvinyl chloride (PVC) RESINS.
28, a kind of at least one surface that comprises internal layer and cover this internal layer is exposed to the outer field composite product of outside atmosphere to prevent internal layer, wherein, described internal layer is by the thermoplastic resin preparation than outer field weathering resistance difference, and described skin is by a kind of formation the in the resin combination of the low surface gloss degree described in the claim 1～23.
29, composite product according to claim 28, wherein, the thermoplastic resin of described internal layer is one or more resins that are selected from acrylonitrile-butadiene-styrene resin and the polyvinyl chloride (PVC) RESINS.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2007-0012861 | 2007-02-07 | ||
| KR1020070012861A KR100889191B1 (en) | 2007-02-07 | 2007-02-07 | Low surface gloss styrene resin composition, low surface gloss sheet containing the same and preparing method thereof |
| KR1020070012861 | 2007-02-07 | ||
| KR10-2007-0094860 | 2007-09-18 | ||
| KR1020070094860A KR101002103B1 (en) | 2007-09-18 | 2007-09-18 | Low surface gloss styrene resin composition, and low surface gloss sheet and composite article therefrom |
| KR1020070094860 | 2007-09-18 | ||
| PCT/KR2008/000559 WO2008096976A1 (en) | 2007-02-07 | 2008-01-30 | Low surface gloss styrene resin composition, and low surface gloss sheet and composite article therefrom |
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| CN101605850A true CN101605850A (en) | 2009-12-16 |
| CN101605850B CN101605850B (en) | 2012-07-04 |
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| CN102453157A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst system for preparing broad-peak/dimodal polyethylene in single reactor |
| CN103648767A (en) * | 2011-04-05 | 2014-03-19 | Lg电子株式会社 | Panel with anti-fingerprint property and manufacturing method thereof |
| CN106977863A (en) * | 2017-05-25 | 2017-07-25 | 东台市美佳包装材料有限公司 | A kind of environmental protection, fastness PVC formulas |
| CN110283387A (en) * | 2019-07-22 | 2019-09-27 | 浙江利帆家具有限公司 | A kind of PP/HDPE furniture composite material and preparation method |
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| MY104125A (en) * | 1988-01-13 | 1994-02-28 | Idemitsu Kosan Co | Styrene-based resin composition. |
| US5216076A (en) * | 1989-01-23 | 1993-06-01 | Hitachi Chemical Company | Low gloss agents, process for production thereof, low gloss thermoplastic resin compositions, and molded articles |
| JP3166788B2 (en) * | 1992-03-04 | 2001-05-14 | 出光興産株式会社 | Styrene resin composition |
| KR100534094B1 (en) * | 2003-06-12 | 2005-12-06 | 제일모직주식회사 | Thermoplastic Styrenic Resin Composition |
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| CN102453157B (en) * | 2010-10-22 | 2014-12-10 | 中国石油化工股份有限公司 | Catalyst system for preparing broad-peak/dimodal polyethylene in single reactor |
| CN103648767A (en) * | 2011-04-05 | 2014-03-19 | Lg电子株式会社 | Panel with anti-fingerprint property and manufacturing method thereof |
| CN103648767B (en) * | 2011-04-05 | 2016-02-10 | Lg电子株式会社 | There is panel and the manufacture method thereof of anti-fingerprint property |
| CN106977863A (en) * | 2017-05-25 | 2017-07-25 | 东台市美佳包装材料有限公司 | A kind of environmental protection, fastness PVC formulas |
| CN110283387A (en) * | 2019-07-22 | 2019-09-27 | 浙江利帆家具有限公司 | A kind of PP/HDPE furniture composite material and preparation method |
| CN110283387B (en) * | 2019-07-22 | 2021-09-10 | 浙江利帆家具有限公司 | PP/HDPE composite material for furniture and preparation method thereof |
| CN110563513A (en) * | 2019-10-23 | 2019-12-13 | 兰州理工大学 | formula of modified coating solution for producing slow release fertilizer |
| CN110563513B (en) * | 2019-10-23 | 2021-08-24 | 兰州理工大学 | Modified coating solution for producing slow release fertilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100889191B1 (en) | 2009-03-17 |
| KR20080073962A (en) | 2008-08-12 |
| CN101605850B (en) | 2012-07-04 |
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