WO2015034285A1 - Polymer resin composition for spectacle frame - Google Patents
Polymer resin composition for spectacle frame Download PDFInfo
- Publication number
- WO2015034285A1 WO2015034285A1 PCT/KR2014/008321 KR2014008321W WO2015034285A1 WO 2015034285 A1 WO2015034285 A1 WO 2015034285A1 KR 2014008321 W KR2014008321 W KR 2014008321W WO 2015034285 A1 WO2015034285 A1 WO 2015034285A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- polyester resin
- resin composition
- polymer resin
- monomer
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000002952 polymeric resin Substances 0.000 title claims abstract description 31
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 31
- 239000004645 polyester resin Substances 0.000 claims abstract description 78
- 229920001225 polyester resin Polymers 0.000 claims abstract description 78
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 60
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 39
- 150000002009 diols Chemical class 0.000 claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 239000012779 reinforcing material Substances 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 230000009477 glass transition Effects 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- -1 aromatic dicarboxylic acids Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920006164 aromatic vinyl copolymer Polymers 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- 230000002787 reinforcement Effects 0.000 claims description 8
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 7
- 229960002479 isosorbide Drugs 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 description 21
- 239000003381 stabilizer Substances 0.000 description 19
- 230000001590 oxidative effect Effects 0.000 description 17
- 238000005886 esterification reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000006068 polycondensation reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000007924 injection Substances 0.000 description 11
- 238000002347 injection Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- UJHQBLMWFLSBQM-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1.CC(=C)C(=O)OCC1CO1 UJHQBLMWFLSBQM-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 7
- 239000011258 core-shell material Substances 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 229920000578 graft copolymer Polymers 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- SVHAMPNLOLKSFU-UHFFFAOYSA-N 1,2,2-trichloroethenylbenzene Chemical compound ClC(Cl)=C(Cl)C1=CC=CC=C1 SVHAMPNLOLKSFU-UHFFFAOYSA-N 0.000 description 3
- FVLTXCPGQRZFBQ-UHFFFAOYSA-N 1-butoxy-4-ethenylbenzene Chemical compound CCCCOC1=CC=C(C=C)C=C1 FVLTXCPGQRZFBQ-UHFFFAOYSA-N 0.000 description 3
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 3
- LCJNYCWJKAWZKZ-UHFFFAOYSA-N 1-prop-1-en-2-ylnaphthalene Chemical compound C1=CC=C2C(C(=C)C)=CC=CC2=C1 LCJNYCWJKAWZKZ-UHFFFAOYSA-N 0.000 description 3
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 3
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 3
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 3
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 3
- 150000008360 acrylonitriles Chemical class 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical compound BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- OBRYRJYZWVLVLF-UHFFFAOYSA-N 1-ethenyl-4-ethoxybenzene Chemical compound CCOC1=CC=C(C=C)C=C1 OBRYRJYZWVLVLF-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- HYKOKFYURVJHKT-UHFFFAOYSA-N 1-ethenyl-4-propoxybenzene Chemical compound CCCOC1=CC=C(C=C)C=C1 HYKOKFYURVJHKT-UHFFFAOYSA-N 0.000 description 2
- KLFWUSCMFSYYOJ-UHFFFAOYSA-N 1-phenyl-2-prop-1-en-2-ylbenzene Chemical group CC(=C)C1=CC=CC=C1C1=CC=CC=C1 KLFWUSCMFSYYOJ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KOQMBAGMXLUQDS-UHFFFAOYSA-N 2-benzhydrylidenepropanedinitrile Chemical group C=1C=CC=CC=1C(=C(C#N)C#N)C1=CC=CC=C1 KOQMBAGMXLUQDS-UHFFFAOYSA-N 0.000 description 2
- DBWWINQJTZYDFK-UHFFFAOYSA-N 2-ethenyl-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(C=C)=C1 DBWWINQJTZYDFK-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002291 germanium compounds Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 0 *C(*)(C(C1(*)N)O)C1O Chemical compound *C(*)(C(C1(*)N)O)C1O 0.000 description 1
- RPSGYSWSCYUXQJ-UHFFFAOYSA-N 1-cyanatoethenyl cyanate Chemical compound N#COC(=C)OC#N RPSGYSWSCYUXQJ-UHFFFAOYSA-N 0.000 description 1
- QYEDLURORBHKDO-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene;1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1.CC1=CC=CC=C1C=C QYEDLURORBHKDO-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LIBOYZGDGVDKKH-UHFFFAOYSA-N 2-(8-methylnonyl)butanedioic acid Chemical compound CC(C)CCCCCCCC(C(O)=O)CC(O)=O LIBOYZGDGVDKKH-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- BSBRGUZPHUELJW-UHFFFAOYSA-N 2-ethenyl-1,4-dimethylbenzene;1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1.CC1=CC=C(C)C(C=C)=C1 BSBRGUZPHUELJW-UHFFFAOYSA-N 0.000 description 1
- NORSCOJMIBLOFM-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(=O)OCCO NORSCOJMIBLOFM-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- ILYSKJPEZAABAA-UHFFFAOYSA-N 2-propoxyethenylbenzene Chemical compound CCCOC=CC1=CC=CC=C1 ILYSKJPEZAABAA-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- SBBQDUFLZGOASY-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C=CC1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 101100014660 Rattus norvegicus Gimap8 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920004747 ULTEM® 1000 Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BHBPJIPGXGQMTE-UHFFFAOYSA-N ethane-1,2-diol;2-methylprop-2-enoic acid Chemical compound OCCO.CC(=C)C(O)=O.CC(=C)C(O)=O BHBPJIPGXGQMTE-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/06—Vinyl aromatic monomers and methacrylates as the only monomers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D12/00—Producing frames
- B29D12/02—Spectacle frames
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- the present invention relates to a polymer resin composition for eyeglass frames, and more particularly, to an environmentally friendly polymer resin composition for eyeglass frames having improved properties such as high transparency, high rigidity, and high heat resistance.
- the material of the spectacle frame can be largely divided into metal and plastic.
- plastic material the characteristics such as transparency, rigidity, heat resistance, dimensional stability, chemical resistance, etc. are important. It is common to be required.
- the Ul tem 1000 has a low impact strength, so that the thickness of the injection molded product becomes brittle (fracture) is easily broken, and the resin itself is not good color and transparency is limited to implement a variety of colors, injection molding silver is relatively high ( 350 to 380 ° C) utility costs increased. Accordingly, it can be processed at a lower temperature than conventional eyeglass frame materials, which can reduce utility costs, and can be manufactured in a process that can increase production efficiency by reducing the abrupt stage with stable shrinkage rate after injection. , Stiffness, heat resistance, dimensional stability, and chemical resistance was required for the study on the resin composition for eyeglass frames excellent. [Content of invention]
- the present invention is to provide a polymer resin composition for eyeglass frames which is environmentally friendly and has excellent transparency, rigidity, heat resistance, dimensional stability, and chemical resistance.
- the polymer resin composition for eyeglass frames includes a polyester resin comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component including dianhydronuclear; And a layered reinforcing material comprising a core comprising a butadiene copolymer, an inner shell containing an acrylate / aromatic vinyl copolymer, and an outer shell containing an aromatic vinyl polymer.
- the content of the layered reinforcing material may be 1% by weight to 20% by weight relative to the total content of the polymer resin composition for eyeglass frames.
- the core is 30% to 100% by weight of butadiene monomer, 0% to 70% by weight of aromatic vinyl monomer, 0% to 10% by weight of copolymerizable vinyl monomer, 0% to 5% by weight of crosslinkable monomer.
- An acrylate / aromatic vinyl copolymer obtained by polymerizing a monomer mixture containing 0% to 20% by weight of a copolymerizable vinyl monomer, wherein the outer shell comprises 10% to 100% by weight of an aromatic vinyl monomer. 0 to 90% by weight of alkyl (meth) acrylate having 1 to 8 carbon atoms of the alkyl group, copolymerizable vinyl monomer 0
- a common monomer compound containing a wt% to 50 wt% can be obtained by polymerization, including the vinyl aromatic polymer.
- the polyester resin a polyester resin having a glass transition temperature of 115 ° C to 125 ° C and a number average molecular weight of 16, 000 to 26,000, and a glass transition temperature of 105 ° C to 115 ° C and a number average Molecular weight from 20, 000 to It may include one or more selected from the group consisting of 30,000 polyester resin.
- the glass transition degree is 115 ° C to 125 ° C and the number average molecular weight of 16, 000 to 26, 000 polyester resin and the glass transition temperature is 105 ° C to 115 ° C and the number average molecular weight 20, 000 to 30 , 000, the weight ratio of the polyester resin may be 0.5: 1 to 5: 1.
- the dicarboxylic acid component contained in the polyester resin may further include one or more selected from the group consisting of aromatic dicarboxylic acid having 8 to 20 carbon atoms and gibbo group dicarboxylic acid having 4 to 20 carbon atoms. Can be.
- the dianhydronuclear is contained in the polyester resin may be isosorbide.
- the content of the dianhydronucleic acid contained in the polyester resin may be 5 mol% to 60 mol% with respect to the total diol component content.
- the diol component contained in the polyester resin may further include one or more selected from the group consisting of compounds represented by the following Chemical Formulas 1, 2 and 3.
- ⁇ , 3 ⁇ 4 and 3 ⁇ 4 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, 3 ⁇ 4 and n 2 are each independently an integer of 0 to 3,
- R 5 , R 6 , R 7 and 3 ⁇ 4 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,
- n is an integer of 1 to 7.
- the diol component contained in the polyester resin may further include 1, 4- cyclonucleic acid di and ethylene glycol.
- a spectacle frame including a molded article of the resin composition for the spectacle frame.
- the spectacle frame manufactured from the resin composition for the spectacle frame according to the present invention is environmentally friendly, and has excellent rigidity, heat resistance, dimensional stability, and chemical resistance, and in particular, is excellent in transparency and enables various coloring and film adhesion during secondary processing. There is an advantage.
- the shrinkage rate reduces the sharpness step, which increases the production efficiency.
- the present invention provides a polyester resin comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component including dianhydronuclear; And an impact reinforcing material comprising a core including butadiene-based co-polymer, an inner layer shell including an acrylate / aromatic vinyl copolymer, and an outer layer shell containing an aromatic vinyl polymer.
- a polymer resin composition for eyeglass frames according to an aspect of the present invention a polyester resin comprising a residue of a dicarboxylic acid component containing terephthalic acid, and a residue of a diol component including a dianhydronuclear; And an impact modifier comprising a core comprising a butadiene copolymer, an inner shell comprising an acrylate / aromatic vinyl copolymer, and an outer shell comprising an aromatic vinyl polymer.
- the plastic material for the spectacle frame is not an environmentally friendly biomaterial, and has a problem of poor impact strength, poor transparency, and poor moldability. Accordingly, the present inventors are polyester resin comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a dial component including dianhydronuclear; And when manufacturing a spectacle frame with a polymer resin composition containing a shock reinforcement of a specific composition, the manufacturing process ' no need to add a separate processing aid or release agent during the injection molding on the surface, lower temperature (20 to 60 than the conventional spectacle frame material It is possible to reduce the utility cost by processing at ° C), and it has the advantage of increasing the production efficiency by reducing the rapid stage with stable shrinkage rate after injection, and also has excellent rigidity, heat resistance, dimensional stability, and chemical resistance. , Especially because of its high transparency, It was confirmed through experiments that the spectacle frame capable of coloring and film attachment, and completed the invention.
- the polymeric resin composition for eyeglass frames according to the present invention includes a polyester resin comprising a residue of a dicarboxylic acid component containing terephthalic acid and a residue of a diol component including dianhydronuclear.
- 'residue' means a certain part or unit included in the chemical reaction and the result and derived from the specific compound when the specific compound participates in the chemical reaction.
- 'residue' means a certain part or unit included in the chemical reaction and the result and derived from the specific compound when the specific compound participates in the chemical reaction.
- Each of 'residue 1 ' or 'residue 1 ' of a diol component means a portion derived from a dicarboxylic acid component or a portion derived from a diol component in a polyester formed by an esterification reaction or a polycondensation reaction.
- the 'dicarboxylic acid component' is a dicarboxylic acid such as terephthalic acid, an alkyl ester thereof (lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) and / or their It is used to include acid anhydrides, and may react with diol to form di carboxyl ic acid moiety such as terephthaloyl moiety.
- the dicarboxylic acid component used for synthesizing the polyester resin includes terephthalic acid, heat resistance, chemical resistance or weather resistance of the polyester resin produced (for example, prevention of molecular weight decrease or sulfur change due to UV) Physical properties such as can be improved.
- the dicarboxylic acid component may further include an aromatic dicarboxylic acid component, an aliphatic dicarboxylic acid component, or a mixture thereof as other dicarboxylic acid components.
- 'other dicarboxylic acid component' means a component other than terephthalic acid among the dicarboxylic acid components.
- the dicarboxylic acid component contained in the polyester resin has carbon number
- It may further include one or more selected from the group consisting of 8 to 20 aromatic dicarboxylic acid and aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
- the aromatic dicarboxylic acid component is 8 to 20 carbon atoms, preferably Aromatic dicarboxylic acids having 8 to 14 carbon atoms, or a mixture thereof.
- aromatic dicarboxylic acid include isophthalic acid, naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 4,4'- stilbendicarboxylic acid, 2, 5-furanedicarboxylic acid, 2,5-thiophene dicarboxylic acid, and the like, but specific examples of the aromatic dicarboxylic acid are not limited thereto.
- the aliphatic dicarboxylic acid component may be an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms, or a mixture thereof.
- the aliphatic dicarboxylic acids include cyclonucleic acid dicarboxylic acids such as 1,4-cyclonucleic acid dicarboxylic acid, 1,3-cyclonucleic acid dicarboxylic acid, phthalic acid, sebacic acid, succinic acid, isodecyl succinic acid, Although there are linear, branched or cyclic aliphatic dicarboxylic acid components such as maleic acid, fumaric acid, adipic acid, glutaric acid, and azelaic acid, specific examples of the aliphatic dicarboxylic acid are not limited thereto.
- the dicarboxylic acid component is 50 to 100 mol 3 ⁇ 4>, preferably 70 to 100 mol% of terephthalic acid; and at least one dicarboxyl selected from the group consisting of aromatic dicarboxylic acid and aliphatic dicarboxylic acid Acids 0-50 mol%, preferably 0-30 mol3 ⁇ 4>; If the content of terephthalic acid in the dicarboxylic acid component is too small or too large, physical properties such as heat resistance, chemical resistance or weather resistance of the polyester resin may be lowered. . Meanwhile, the diol component used in the synthesis of the polyester resin may include 5 to 60 mol% of dianhydronuclear, 5 to 80 mol% of dimethyl methane, and the remaining amount of other diol compounds. Can be.
- the diol component preferably includes isosorbide (1,4: 3,6—dianhydroglucitol) as dianhydronuclear
- isosorbide (1,4: 3,6—dianhydroglucitol) as dianhydronuclear
- the content of cyclonucleodimethanol increases in the diol component.
- the polyester produced The impact strength of the resin can be greatly increased.
- the diol component may further include other dial components in addition to the isosorbide and cyclonucleic acid dimethane.
- the 'other diol component' refers to a diol component other than the isosorbide and cyclonucleodimethane, and may be, for example, aliphatic di, aromatic di, or a combination thereof.
- the diol component included in the polyester resin may further include one or more selected from the group consisting of compounds represented by the following Chemical Formulas 1, 2 and 3.
- R 4 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, ⁇ and n 2 are each independently an integer of 0 to 3,
- R 5 , R 7 and 3 ⁇ 4 are each independently hydrogen or a substituted or unsubstituted white group having 1 to 5 carbon atoms,
- n is an integer of 1 to 7.
- the polyester resin is a dicarboxylic acid containing a dial component and terephthalic acid containing 5 to 80 mol% of dianhydronucleoisoisosorbide 5 to 60 mol cyclohexamethane dimethane and a balance of other diol compounds Esterifying the components; Adding to the "phosphorus-containing stabilizer at the time of esterification is conducted banung than 80%; And it may be provided by a method for producing a polyester resin comprising the step of polycondensation reaction of the esterified reaction product.
- an esterification reaction catalyst containing a zinc-based compound is used, and at the end of the esterification reaction, for example, a phosphorus stabilizer is added to the reaction mixture at the time when reaction reaction proceeds by 80% or more.
- a polyester resin exhibiting physical properties such as high heat resistance, flame retardant properties and impact resistance having excellent appearance characteristics, high transparency and excellent molding properties. Details of the dicarboxylic acid component, cyclonucleic acid dimethanol, isosorbide and other diol compounds containing terephthalic acid are as described above.
- the esterification reaction step may be accomplished by reacting the dicarboxylic acid component and the diol component at a pressure of 0 to 10.0 kg / crf and at 150 to 300 ° C. silver.
- the esterification reaction conditions can be appropriately adjusted according to the specific properties of the polyester resin to be produced, the molar ratio of the dicarboxylic acid component and glycol, or process conditions. Specifically, preferred examples of the esterification conditions, 0 to 5.0 kg / cin 2 , more preferably 0.1 to 3.0 kg / cm 2 pressure; 200 to 270 ° C., more preferably 240 to 260 ° C. may be mentioned.
- the esterification reaction can be carried out in a batch (batch) or continuous, each and the raw material may be added separately, but the diol component It is preferable to add the dicarboxylic acid component in the form of a mixed slurry.
- the diol component such as dianhydrohex, which is a solid content at room temperature, may be dissolved in water or ethylene glycol, and then mixed with a dicarboxylic acid component such as terephthalic acid to form a slurry. After the black melts the dianhydronuclears at 60 ° C. or higher, the slurry can also be prepared by mixing a dicarboxylic acid component such as tetephthalic acid and other dial components.
- water may be further added to a slurry in which a dicarboxylic acid component, a dianhydronucleic acid, and a copolymerized diol component such as ethylene glycol are mixed to help increase the fluidity of the slurry.
- the molar ratio of the dicarboxylic acid component and the diol component participating in the esterification reaction may be 1: 1.05 to 1: 3.0.
- the molar ratio of the dicarboxylic acid component: diol component is less than 1.05, unreacted dicarboxylic acid component may remain during polymerization reaction, thereby decreasing transparency of the polyester resin, and when the molar ratio exceeds 3.0, polymerization reaction The speed may be lowered or the productivity of the resin may be lowered.
- the poly-condensat ion reaction of the esterified reaction product may include reacting the esterification product of the dicarboxylic acid component and the diol component at 150 to 300 ° C. and a reduced pressure of 600 to 0.01 mmHg. And reacting for 24 hours.
- Such polycondensation reaction is, 150 to 300 ° C, preferably 200 to
- the polycondensation reaction occurs outside the temperature range of 150 to 300 ° C, if the condensation polymerization reaction proceeds below 150 ° C, the intrinsic viscosity of the final reaction product may not be effectively removed from the system as a glycol by-product of the polycondensation reaction Low physical properties of the polyester resin may be lowered, When the reaction proceeds to 300 ° C or more, the appearance of the polyester resin produced becomes more likely to be yellowing. The polycondensation reaction can then proceed for the required time until the intrinsic viscosity of the final reaction product reaches an appropriate level, for example for an average residence time of 1 to 24 hours.
- the production method of the polyester resin composition may further comprise the step of further adding a polycondensation catalyst.
- the polycondensation catalyst is added to the heunhap slurry containing dieul component and the dicarboxylic acid component the esterification may be added to the reaction, or the product of the transesterification, the esterification reaction "before prior to the start of the polycondensation banung It may be added to the esterification reaction step illustration. ⁇
- titanium compound a germanium compound, an antimony compound, an aluminum-based compound, tin compound or a common compound.
- examples of the titanium compound and the germanium compound are as described above.
- the polyester resin the glass transition degree is 115 ° C to 125 ° C, or 118 ° C to 122 ° C and the number average molecular weight of 16,000 to 26,000, or 20,000 to 24,000, or 21,000 to 23,000
- Ester resin polyester resin having a glass transition temperature of 105 ° C to 115 ° C, or 108 ° C to 122 ° C and a number average molecular weight of 20, 000 to 30,000, or 23,000 to 26,000, or 23,500 to 25, 500 or Combinations thereof.
- the glass transition temperature is 115 ° C to 125 ° C
- the polyester resin and the glass transition temperature is 105 ° C to a number average molecular weight of 16,000 to 26,000
- the weight ratio of the polyester resin having a 115 ° C. and a number average molecular weight of 20,000 to 30, 000 may be 0.5: 1 to 5: 1, or 0.5: 1 to 1: 1, or 1: 1 to 3: 1.
- the glass transition temperature is 115 ° C to 125 ° C and the number average molecular weight 16,000
- the polyester resin of 2 to 26, 000 and the polyester resin having a glass transition temperature of 105 ° C to 115 ° C and a number average molecular weight of 20,000 to 30,000 in the above-described specific content May have improved properties such as high transparency, high stiffness, and high thermal conductivity.
- the polyester resin having a glass transition temperature of 115 ° C to 125 ° C and a number average molecular weight of 16,000 to 26,000, and a glass transition temperature of 105 ° C to 115 ° C and a number average molecular weight of 20,000 to 30,
- the weight ratio of the polyester resin of 000 is less than 0.5: 1
- the glass transition temperature is 115 ° C to 125 ° C and the content of the polyester resin having a number average molecular weight of 16,000 to 26,000 is excessively reduced
- the polymer resin for eyeglass frames The heat resistance of the composition may decrease.
- the polyester resin having a glass transition temperature of 115 ° C to 125 ° C and a number average molecular weight of 16,000 to 26,000, and a polyamide having a glass transition degree of 105 ° C to 115 ° C and a number average molecular weight of 20,000 to 30, 000
- the increase ratio of the ester resin is 5: 1
- the content of the polyester resin having a glass transition temperature of 105 ° C to 115 ° C and a number average molecular weight of 20,000 to 30,000 is excessively reduced, so that the polymer resin composition for eyeglass frames Molecular weight may be reduced, and accordingly, mechanical properties of the polymer resin composition for eyeglass frames, for example, layer resistance, rigidity, elastic modulus, and the like may be reduced.
- the polymer resin composition for eyeglass frames according to the present invention may include an impact reinforcing material including a core including a butadiene copolymer, an inner layer shell including an acrylate / aromatic vinyl copolymer, and an outer layer shell containing an aromatic vinyl polymer; .
- the core of the impact modifier according to the invention is 30% to 100% by weight, preferably 40% to 90% by weight, more preferably 50% to 80% by weight.
- butadiene-based copolymers obtained by polymerizing a monomeric mixture containing a copolymerizable vinyl monomer and a monomer mixture containing 0 wt% to 5 wt% of a crosslinkable monomer.
- butadiene monomers is preferable in terms of strength, it is separated from the refractive index of the polyester resin comprising residues of dicarboxylic acid components including amorphous terephthalic acid and residues of diol components including dianhydronuclear. It is preferable to set it as weight% or less from a transparency point. Moreover, since it is possible to obtain excellent strength expression power by setting it to 40 weight% or more, it is preferable. More preferably, it is used at 50% by weight to 80% by weight.
- Aromatic vinyl monomers are compounds having one vinyl double bond and one or more benzene nuclei in the same molecule, specifically styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4 -Ethyl styrene, 2, 5-dimethyl styrene 4-methoxy styrene, 4-especial styrene, 4-propoxy styrene, 4-butoxy styrene, chloro styrene, dichloro styrene, trichloro styrene, vinylluene, bromostyrene And aromatic vinyl monomers such as dibromostyrene, tmobromostyrene, vinyl naphthalene, isopropenyl naphthalene, isopropenyl biphenyl, divinylvangen, and the like, but are not limited thereto.
- the refractive index of the rubber particles increases the refractive index of the rubber particles and approaches the refractive index of the polyester resin including residues of the dicarboxylic acid component including amorphous terephthalic acid and residues of the diol component including dianhydronuclear. It is preferable to use at least 20% by weight or more, and in terms of transparency, and to use the aromatic vinyl monomer at 60% by weight or less, preferably 50% by weight or less, since the strength is maintained.
- vinyl monomers copolymerizable include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate.
- Vinyl cyanide compounds such as nitrile, (meth) acrylic acid, phenyl (meth) acrylate, vinylidene cyanide, 1,2-dicyanoethylene, maleimide compounds, and the like.
- crosslinkable monomer examples include divinyl acrylate divinylbenzene monoethylene glycol, dimethacrylate ethylene glycol, and the like, but are not limited thereto.
- Crosslinkable monomer ' sieve is used in the range of 0% by weight to 5% by weight because the impact strength is lowered when used in excess of 5% by weight.
- the inner shell of the layered reinforcement according to the present invention is 60% to 98% by weight, preferably 65% to 95% by weight of an aromatic vinyl monomer, 2% by weight; to 40% by weight, preferably 5% by weight to 35%.
- Acrylate / aromatic obtained by combining a monomer containing a (meth) acrylic acid ester containing a weight percent hydroxyl group or an alkoxy group, and a monomer mixture containing 0 weight percent to 20 weight percent vinyl monomer copolymerizable with these.
- Vinyl copolymers obtained by combining a monomer containing a (meth) acrylic acid ester containing a weight percent hydroxyl group or an alkoxy group, and a monomer mixture containing 0 weight percent to 20 weight percent vinyl monomer copolymerizable with these.
- 'acrylate / aromatic vinyl copolymer' means a copolymer obtained by polymerizing a mixture of an acrylate monomer and an aromatic vinyl monomer.
- the aromatic vinyl monomer forming the inner shell is a compound having one vinyl double bond and at least one benzene nucleus in the same molecule, specifically styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4 -Methyl styrene, 4-ethyl styrene, 2, 5- dimethyl styrene, 4- methoxy styrene, 4- ethoxy styrene, 4 ⁇ propoxy styrene, 4- butoxy styrene, chloro styrene, dichloro styrene, trichloro styrene, Aromatic vinyl monomers such as vinylluene, bromostyrene
- Monomers containing a (meth) acrylic acid ester containing a hydroxyl group or an alkoxy group include hydroxyethyl acrylate, Hydroxypropyl acrylate, alkoxy acrylate such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, methoxyethyl acrylate, ecoxyethyl acrylate, etc.
- alkoxy methacrylates such as methacrylate hydroxyethyl methacrylate, etc. are mentioned, It is not limited to these.
- the use of these in the inner layer shell improves the interfacial adhesion between the polyester resin containing the residue of the polycarboxylic acid component including amorphous terephthalic acid and the residue of the dial component including dianhydronuclear, and the core shell modifier. desirable.
- the viscosity at the time of melt mixing does not become high, it is preferable.
- vinyl monomers copolymerizable include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate,
- the outer shell used for the layered reinforcement according to the present invention comprises 10% to 100% by weight of aromatic vinyl monomer, 0% to 90% by weight of alkyl (meth) acrylate;
- An aromatic vinyl polymer obtained by polymerizing a monomer mixture containing 0 wt% to 50 wt% of a copolymerizable vinyl monomer may be included.
- the alkyl group may include a linear or branched alkyl group having 1 to 8 carbon atoms, and the alkyl (meth) acrylate may be an ester compound of acrylic acid or methacrylic acid, Examples include, but are not limited to, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and the like. The use of these is based on the residues of the dicarboxylic acid component containing amorphous terephthalic acid and the diol component containing dianhydronuclear.
- Aromatic vinyl monomers include, for example, styrene, ⁇ -methylstyrene, 2-methylstyrene 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 2, 5-dimethylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4-propoxystyrene, 4-butoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, vinylluene, bromostyrene, dibromostyrene, tribromostyrene, vinylnaphthalene, isopropenyl naphthalene, isopropenyl Aromatic vinyl monomers, such as biphenyl, etc.
- the use of these is preferable in terms of transparency because it increases the refractive index of the shell and approaches the refractive index of the polyester resin containing the residue of the dicarboxylic acid component including amorphous terephthalic acid and the dial component including dianhydronuclear.
- the copolymerizable monomer include acrylic acid, methacrylic acid, methacrylonitrile, acrylonitrile, vinylidecyanate, vinyl cyanide compounds such as 1,2-dicyanoethylene, maleimide compounds, and the like. It doesn't happen.
- the inner shell is the polyester containing the residues of the dicarboxylic acid component including dianhydronuclear and the residues of the dicarboxylic acid component including amorphous terephthalic acid
- Approaching the refractive index of the resin is to improve the interfacial adhesion between the polyester resin comprising the residue of the dicarboxylic acid component containing amorphous terephthalic acid and the residue of the diol component including dianhydronuclear, and the core shell modifier.
- the particle diameter of the layered reinforcing material is not particularly limited, but the degree of improvement of the impact strength is large at 0.0 / m or more, and transparency is secured at 0.5 / im or less, so it is preferably 0.05 to 0.0 m.
- a method for preparing the particle diameter of the butadiene-based copolymer As a method for preparing the particle diameter of the butadiene-based copolymer, a method of increasing the size during graft polymerization using a water-soluble electrolyte disclosed in Japanese Patent Publication No. 43-12158, or as disclosed in JP-A-8-012704 same
- the method of using the acidic radical containing latex which consists of a copolymer of (meth) acrylic acid ester and unsaturated acid can also be used.
- the particle diameter of the core included in the layered reinforcing material is not particularly limited, but if it is 0.05 / or more, the degree of improvement in impact strength is large, and if it is 0.01 or less, transparency is ensured, 0.05, to 0.1, or It is preferable that it is 0.06-0.08 / im.
- the impact reinforcing material according to the present invention can be obtained in emulsion polymerization, suspension polymerization, solution polymerization, etc., but emulsion polymerization is preferred.
- the emulsion polymerization is produced by a known emulsion method or polymerization procedure.
- the content of the impact reinforcing material may be 1% by weight to 20% by weight, or 5% by weight to 15% by weight, or 8% by weight to 12% by weight with respect to the total content of the polymer resin composition for eyeglass frames.
- the content of the layered reinforcing material is less than 1% by weight, the effect of improving the layered resistance by the impact reinforcing material may be reduced.
- the content of the layered reinforcing material is more than 20% by weight, transparency may be reduced to various colors. Problems may occur that the colorability may be lowered.
- a spectacle frame including a molded article of the resin composition for the spectacle frame.
- the spectacle frame may include a molded article manufactured by molding the resin composition for the spectacle frame.
- the molded article may be formed using various molding methods such as injection molding, extrusion, extrusion blow, injection blow, profile extrusion, and post-processing such as thermoforming using the same. It can be obtained by molding through.
- Specific shape or size of the molded article can be determined in various ways depending on the application, the example is not particularly limited.
- the spectacle frame may further include a metal, a pigment, and the like together with the molded article of the resin composition for the spectacle frame.
- the metal or pigment may be used without limitation as long as it is commonly used in the field of eyeglass frame manufacturing, and examples thereof are not particularly limited.
- preferred embodiments of the present invention will be described in detail. However, these Examples are only for illustrating the present invention, and the scope of the present invention is not to be construed as being limited by these Examples.
- terephthalic acid-isosorbide-1, 4-cyclonucleodiol diol-ethylene glycol copolymerized polyester resin is eco-enzyme (EC0ZEN), methyl methacrylate-butadiene-styrene graft air M-300, acrylonitrile-styrene-glycidyl methacrylate, a graft MBS product in the form of a core-shell rubber (Core-She 11 1 Rubber) manufactured by KANEKA, Japan, is SAG-005, a phenolic system of SUNNY FC of China.
- As the primary oxidative stabilizer AADEO 60 from ADEKA, Japan, and the phosphite secondary oxidative stabilizer were used as Igar fos 168 from Cl ar i ant, Switzerland.
- terephthalic acid-isosorbide-1, 4-cyclonucleic acid di- ethylene glycol copolymerized polyester resin is Eco-Zen (EC0ZEN), methyl methacrylate-butadiene-styrene graft air M-300, acrylonitrile-styrene-glycidyl methacrylate, a graft MBS product in the form of a core-shell rubber of KANEKA, Japan, is SAG-005, phenolic 1, manufactured by SUNNY FC of China.
- the primary oxidative stabilizer was AO-60 from ADEKA, Japan
- the phosphite-based secondary oxidative stabilizer was from Igarfos 168 from Cl ar i ant, Switzerland.
- terephthalic acid-isosorbide-1,4-cyclonucleic acid di- ethylene glycol copolymerized polyester resin is Eco-Zen (EC0ZEN), methyl methacrylate-butadiene-styrene graft air
- the coalescing is made of M-300, acrylonitrile-styrene, a graft MBS product in the form of core-shell rubber (KANEKA, Japan). Glycidyl methacrylate is China.
- Tg 120 ° C,
- terephthalic acid-isosorbide-1, 4-cyclonucleodiol diol-ethylene glycol copolymerized polyester resin is eco-enzyme (EC0ZEN), methyl methacrylate-butadiene-styrene graft air Incorporation of M-300, acrylonitrile-styrene-glycidyl methacrylate, a graft MBS product in the form of core-shell rubber of KANEKA, Japan, is SAG-005, phenolic 1 of SUNNY FC of China.
- the primary oxidative stabilizer was A0-60 from ADEKA, Japan, and the S-9228 from DOVER, USA, was used as a phosphite secondary oxidative stabilizer.
- terephthalic acid-iso carbide-1, 4-cyclonucleodiol diol-ethylene glycol copolymerized polyester resin is Eco-Zen (EC0ZEN), methyl methacrylate-butadiene-styrene graft air Incorporation of M-300, acrylonitrile styrene-glycidyl methacrylate, a graft MBS product in the form of Core-Shell Rubber of RANEKA, Japan, is SAG-005, phenolic 1 of SUNNY FC of China.
- the primary oxidative stabilizer was A0-60 from ADEKA, Japan, and the S-9228 from DOVER, USA, was used as a phosphite secondary oxidative stabilizer. Comparative Examples 1 to 4
- the conventional plastic product for eyeglass frames was compared as follows.
- test specimens were made and the transparency was measured using a turbidimeter (Hazemeter, Denshoku).
- the spectacle frames of Examples 1 to 5 may be confirmed to be an excellent eco-friendly material that can realize the properties similar to those of the conventional spectacle frames, while including environmentally friendly non-resin.
- the Izod layer strength was measured to be 800 J / m or more, showing that the Izod impact strength is significantly improved compared to the spectacle frame of Comparative Examples 1 to 4 with less than 700 J / m. You can check it. Accordingly, in the case of the spectacle frames of Examples 1 to 5, even if the thickness is thin may exhibit a characteristic that is not easily broken.
Abstract
The present invention relates to a polymer resin composition for a spectacle frame which is environment-friendly and has improved properties, such as high transparency, high stiffness, high thermal resistance, etc. The polymer resin composition for a spectacle frame in accordance with an aspect of the invention comprises: a polyester resin comprising a residue of a dicarboxylic acid component comprising terephthalic acid and a residue of a diol component comprising dianhydrohexitol; and an impact reinforcing material comprising a core comprising butadiene-based copolymer, an inner layer shell comprising acrylate/aromatic vinly copolymer, and an outer layer shell comprising aromatic vinyl-based polymer.
Description
【명세서】 【Specification】
【발명의 명칭】 [Name of invention]
안경테용 고분자 수지 조성물 Polymer resin composition for eyeglass frames
[기술분야] [Technical Field]
본 발명은 안경테용 고분자 수지 조성물에 관한 것으로 보다 상세하게는 환경 친화적이면서 고투명성， 고강성， 고내열성 등의 향상된 특성을 가지는 안경테용 고분자 수지 조성물에 관한 것이다. The present invention relates to a polymer resin composition for eyeglass frames, and more particularly, to an environmentally friendly polymer resin composition for eyeglass frames having improved properties such as high transparency, high rigidity, and high heat resistance.
【발명의 배경이 되는 기술】 [Technique to become background of invention]
안경테의 재질은 크게 금속과 플라스틱으로 나눌 수 있는데， 플라스틱 소재의 경우 소재의 투명성， 강성 , 내열성， 치수안정성， 및 내화학약품성 등의 특성이 중요하고， 성형 시 가공의 용이성， 및 생산 효율성 등이 요구되는 것이 일반적이다. The material of the spectacle frame can be largely divided into metal and plastic. In the case of plastic material, the characteristics such as transparency, rigidity, heat resistance, dimensional stability, chemical resistance, etc. are important. It is common to be required.
한편， 안경테용 플라스틱 소재 중 대표적인 것으로 스위스 EMS Gr ivory ' TR-90 ' , SABIC ' Ul tem 1000 ' 등이 알려져 있는데， 이들은 공통적으로 바이오 수지가 아니어서 환경친화적이지 않다는 문제가 있었다. 아울러， TR-90은 노치충격강도가 좋지 아니하고， 사출성형 작업 시 성형성이 좋지 않아 사출업체에서 별도로 이형제를 첨가해야 하며， 수지 자체 색상과 투명도가 좋지 않아 다양한 색상 구현이 제한되고， 사출 후 수축율이 높아 급냉 프로세스를 반드시 거쳐야 한다는 단점이 있었고， 또한 사출 가공 온도가 상대적으로 높아 (250 내지 260°C ) 유틸리티 비용이 증가한다는 문제점이 있었다. On the other hand, representative plastic materials for eyeglass frames are known as Switzerland EMS Gr ivory 'TR-90', SABIC 'Ultem 1000', and these are not bio-resistive, so they are not environmentally friendly. In addition, TR-90 does not have good notch impact strength, and it is not good moldability during injection molding work, so the release company needs to add a release agent separately, and the color of resin itself is not good and transparency is limited, and various colors are limited. This has the disadvantage of having to go through a quenching process, and also has a problem that the injection cost is relatively high (250 to 260 ° C) utility costs increase.
한편， 상기 Ul tem 1000는 충격강도가 좋지 않아 사출성형품의 두께가 얇아지면 취성 ( fracture)이 생겨 쉽게 부러지고， 수지 자체 색상과 투명도가 좋지 않아 다양한 색상 구현아 제한되며， 사출 가공 은도가 상대적으로 높아 (350 내지 380°C ) 유틸리티 비용 증가한다는 단점이 있었다. 이에 따라， 기존 안경테용 소재 대비 낮은 온도에서 가공이 가능하여 유틸리티 비용 절감이 가능하고， 사출 후 안정적 수축율로 급넁 단계가 감소하여 생산 효율성을 증가시킬 수 있는 공정으로 제조될 수 있는， 최종 소재의 투명성， 강성， 내열성， 치수안정성， 및 내화학약품성이 우수한 안경테용 수지 조성물에 대한 연구가 필요한 실정이었다.
【발명의 내용】 On the other hand, the Ul tem 1000 has a low impact strength, so that the thickness of the injection molded product becomes brittle (fracture) is easily broken, and the resin itself is not good color and transparency is limited to implement a variety of colors, injection molding silver is relatively high ( 350 to 380 ° C) utility costs increased. Accordingly, it can be processed at a lower temperature than conventional eyeglass frame materials, which can reduce utility costs, and can be manufactured in a process that can increase production efficiency by reducing the abrupt stage with stable shrinkage rate after injection. ， Stiffness, heat resistance, dimensional stability, and chemical resistance was required for the study on the resin composition for eyeglass frames excellent. [Content of invention]
【해결하고자 하는 과제】 Problem to be solved
본 발명은 환경 친화적이면서， 우수한 투명성， 강성， 내열성， 치수안정성, 및 내화학약품성을 가지는 안경테용 고분자 수지 조성물을 제공하는 것이다. The present invention is to provide a polymer resin composition for eyeglass frames which is environmentally friendly and has excellent transparency, rigidity, heat resistance, dimensional stability, and chemical resistance.
【과제의 해결 수단】 [Measures of problem]
본 발명의 일 측면에 따른 안경테용 고분자 수지 조성물은, 테레프탈산을 포함한 디카르복실산 성분의 잔기와， 디안히드로핵시를을 포함한 디올 성분의 잔기를 포함하는 폴리에스테르 수지; 및 부타디엔계 공중합체를 포함한 코어， 아크릴레이트 /방향족 비닐 공중합체를 포함한 내층 쉘 및 방향족 비닐계 고분자를 포함한 외층 쉘을 포함하는 층격 보강재；를 포함한다 . The polymer resin composition for eyeglass frames according to an aspect of the present invention includes a polyester resin comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component including dianhydronuclear; And a layered reinforcing material comprising a core comprising a butadiene copolymer, an inner shell containing an acrylate / aromatic vinyl copolymer, and an outer shell containing an aromatic vinyl polymer.
그리고, 상기 층격 보강재의 함량이 전체 안경테용 고분자 수지 조성물 함량에 대하여 1 중량 % 내지 20 중량 %일 수 있다. In addition, the content of the layered reinforcing material may be 1% by weight to 20% by weight relative to the total content of the polymer resin composition for eyeglass frames.
또한， 상기 코어는 부타디엔 단량체 30 중량 % 내지 100 중량 %， 방향족 비닐 단량체 0 중량 % 내지 70 중량 %， 공중합가능한 비닐계 단량체 0 중량 % 내지 10 중량 %， 가교성 단량체 0 중량 % 내지 5 증량 %를 함유하는 단량체 흔합물을 중합하여 얻어지는 부타디엔계 공중합체를 포함하고, 상기 내층 쉘은 방향족 비닐 단량체 60 중량 % 내지 98 증량 % , 히드록실기를 함유하는 (메타)아크릴산에스테르 단량체 2 중량 % 내지 40 중량 %， 공중합가능한 비닐계 단량체 0 중량 % 내지 20 중량 %를 함유하는 단량체 흔합물을 중합하여 얻어지는 아크릴레이트 /방향족 비닐 공중합체를 포함하며， 상기 외층 쉘은 방향족 비닐 단량체 10 중량 % 내지 100 중량 %， 알킬기의 탄소수 1 내지 8 의 알킬 (메타)아크릴레이트 0 중량 % 내지 90 중량 %， 공중합가능한 비닐계 단량체 0 중량 % 내지 50 중량 %를 함유하는 단량체 흔합물을 중합하여 얻어지는 방향족 비닐계 고분자를 포함할 수 있다. In addition, the core is 30% to 100% by weight of butadiene monomer, 0% to 70% by weight of aromatic vinyl monomer, 0% to 10% by weight of copolymerizable vinyl monomer, 0% to 5% by weight of crosslinkable monomer. A butadiene-based copolymer obtained by polymerizing a monomer mixture to be contained, wherein the inner shell includes 60% by weight to 98% by weight of an aromatic vinyl monomer, and 2% by weight to 40% by weight of a (meth) acrylic acid ester monomer containing a hydroxyl group. %, An acrylate / aromatic vinyl copolymer obtained by polymerizing a monomer mixture containing 0% to 20% by weight of a copolymerizable vinyl monomer, wherein the outer shell comprises 10% to 100% by weight of an aromatic vinyl monomer. 0 to 90% by weight of alkyl (meth) acrylate having 1 to 8 carbon atoms of the alkyl group, copolymerizable vinyl monomer 0 A common monomer compound containing a wt% to 50 wt% can be obtained by polymerization, including the vinyl aromatic polymer.
아울러， 상기 폴리에스테르 수지는， 유리전이온도가 115°C 내지 125°C이고 수평균분자량이 16 , 000 내지 26 , 000인 폴리에스테르 수지 및 유리전이온도가 105 °C 내지 115°C이고 수평균분자량이 20 , 000 내지
30 , 000인 폴리에스테르 수지로 이루어진 군으로부터 선택되는 하나 이상을 포함할 수 있다. In addition, the polyester resin, a polyester resin having a glass transition temperature of 115 ° C to 125 ° C and a number average molecular weight of 16, 000 to 26,000, and a glass transition temperature of 105 ° C to 115 ° C and a number average Molecular weight from 20, 000 to It may include one or more selected from the group consisting of 30,000 polyester resin.
상기 유리전이은도가 115°C 내지 125°C이고 수평균분자량이 16 , 000 내지 26 , 000인 폴리에스테르 수지 및 유리전이온도가 105°C 내지 115°C이고 수평균분자량이 20 , 000 내지 30 , 000인 폴리에스테르 수지의 중량비가 0.5 : 1 내지 5 : 1일 수 있다. The glass transition degree is 115 ° C to 125 ° C and the number average molecular weight of 16, 000 to 26, 000 polyester resin and the glass transition temperature is 105 ° C to 115 ° C and the number average molecular weight 20, 000 to 30 , 000, the weight ratio of the polyester resin may be 0.5: 1 to 5: 1.
한편， 상기 폴리에스테르 수지에 포함된 디카르복실산 성분은 탄소수 8 내지 20의 방향족 디카르복^산 및 탄소수 4 내지 20의 지밥족 디카르복실산으로 이루어진 군으로부터 선택되는 1종 이상을 더 포함할 수 있다. On the other hand, the dicarboxylic acid component contained in the polyester resin may further include one or more selected from the group consisting of aromatic dicarboxylic acid having 8 to 20 carbon atoms and gibbo group dicarboxylic acid having 4 to 20 carbon atoms. Can be.
그리고， 상기 폴리에스테르 수지에 포함된 디안히드로핵시를은 아이소소바이드 일 수 있다. And, the dianhydronuclear is contained in the polyester resin may be isosorbide.
또한, 상기 폴리에스테르 수지에 포함된 디안히드로핵시를의 함량은 전체 디올 성분의 함량에 대하여 5 몰% 내지 60 몰%일 수 있다. In addition, the content of the dianhydronucleic acid contained in the polyester resin may be 5 mol% to 60 mol% with respect to the total diol component content.
. 아울러， 상기 폴리에스테르 수지에 포함된 디올 성분은 하기 화학식 1， 2 및 3으로 표시되는 화합물들로 이루어진 군으로부터 선택되는 1종 이상을 더 포함할 수 있다. . In addition, the diol component contained in the polyester resin may further include one or more selected from the group consisting of compounds represented by the following Chemical Formulas 1, 2 and 3.
[화학식 1] [Formula 1]
상기 화학식 1에서, ！^， ， ¾ 및 ¾ 는 각각 독립적으로 수소 또는 탄소수 1 내지 5 의 치환 또는 비치환된 알킬기이며， ¾ 및 n2 는 각각 독립적으로 0 내지 3의 정수이고， In Formula 1,！ ^, ¾ and ¾ are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, ¾ and n 2 are each independently an integer of 0 to 3,
[화학식 2]
[Formula 2]
상기 화학식 2에서 , R5 , R6 , R7 및 ¾는 각각 독립적으로 수소 또는 탄소수 1 내지 5 의 치환 또는 비치환된 알킬기이며， In Formula 2, R 5 , R 6 , R 7 and ¾ are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,
[화학식 3]
상기 화학식 3에서, n 은 1 내지 7의 정수이다. [Formula 3] In Formula 3, n is an integer of 1 to 7.
한편， 상기 폴리에스테르 수지에 포함된 디올 성분은 1 , 4- 사이클로핵산디을 및 에틸렌글리콜을 더 포함할 수 있다. On the other hand, the diol component contained in the polyester resin may further include 1, 4- cyclonucleic acid di and ethylene glycol.
본 발명의 또 다른 측면에 따르면 상기 안경테용 수지 조성물의 성형품을 포함하는 안경테가 제공될 수 있다. According to another aspect of the present invention may be provided with a spectacle frame including a molded article of the resin composition for the spectacle frame.
【발명의 효과】 【Effects of the Invention】
본 발명에 따른 안경테용 수지 조성물로부터 제조된 안경테는 환경 친화적이면서， 강성， 내열성， 치수안정성， 및 내화학약품성이 우수하고， 특히 투명성이 우수하여 2차 가공 시 다양한 착색 및 필름 부착 등이 가능하다는 장점이 있다. 또한， 제조 공정면에서， 사출성형 시 별도의 가공조제 또는 이형제 첨가가 불필요하고， 기존 안경테용 소재 대비 낮은 은도 (20 내지 60°C )에서 가공이 가능하여 유틸리티 비용 절감이 가능하며， 사출 후 안정적 수축율로 급넁 단계가 감소하여 생산 효율성이 증가하는 장점이 있다. The spectacle frame manufactured from the resin composition for the spectacle frame according to the present invention is environmentally friendly, and has excellent rigidity, heat resistance, dimensional stability, and chemical resistance, and in particular, is excellent in transparency and enables various coloring and film adhesion during secondary processing. There is an advantage. In addition, in the manufacturing process, it is not necessary to add a separate processing aid or release agent during injection molding, and it is possible to process at a lower silver (20 to 60 ° C) than conventional materials for eyeglass frames, thereby reducing utility costs and stable after injection. The shrinkage rate reduces the sharpness step, which increases the production efficiency.
【발명을 실시하기 위한 구체적인 내용】 [Specific contents to carry out invention]
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 상세한 설명에 상세하게 설명하고자 한다. 그러나， 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며， 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을
포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다. 본 발명은， 테레프탈산을 포함한 디카르복실산 성분의 잔기와， 디안히드로핵시를을 포함한 디올 성분의 잔기를 포함하는 폴리에스테르 수지; 및 부타디엔계 공증합체를 포함한 코어， 아크릴레이트 /방향족 비닐 공중합체를 포함한 내층 쉘 및 방향족 비닐계 고분자를 포함한 외층 쉘을 포함하는 충격 보강재；를 포함하는 안경테용 고분자 수지 조성물을 제공한다. As the invention allows for various changes and numerous embodiments, particular embodiments will be described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and all modifications, equivalents, and substitutes included in the spirit and technical scope of the present invention are not included. It should be understood to include. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted. The present invention provides a polyester resin comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component including dianhydronuclear; And an impact reinforcing material comprising a core including butadiene-based co-polymer, an inner layer shell including an acrylate / aromatic vinyl copolymer, and an outer layer shell containing an aromatic vinyl polymer.
이하 발명의 구체적인 구현예에 따른 안경테용 고분자 수지 조성물에 관하여 보다 상세하게 설명하기로 한다 . 본 발명의 일 측면에 따른 안경테용 고분자 수지 조성물은， 테레프탈산을 포함한 디카르복실산 성분의 잔기와， 디안히드로핵시를을 포함한 디올 성분의 잔기를 포함하는 폴리에스테르 수지; 및 부타디엔계 공중합체를 포함한 코어， 아크릴레이트 /방향족 비닐 공중합체를 포함한 내층 쉘 및 방향족 비닐계 고분자를 포함한 외층 쉘을 포함하는 충격 보강재；를 포함한다. Hereinafter, the polymer resin composition for eyeglass frames according to a specific embodiment of the present invention will be described in detail. A polymer resin composition for eyeglass frames according to an aspect of the present invention, a polyester resin comprising a residue of a dicarboxylic acid component containing terephthalic acid, and a residue of a diol component including a dianhydronuclear; And an impact modifier comprising a core comprising a butadiene copolymer, an inner shell comprising an acrylate / aromatic vinyl copolymer, and an outer shell comprising an aromatic vinyl polymer.
종래 안경테용 플라스틱 소재는 친환경적인 바이오 소재가 아니고， 충격강도가 좋지 않으며, 투명성， 성형성이 좋지 않은 등의 문제점이 있었다. 이에 본 발명자들은 테레프탈산을 포함한 디카르복실산 성분의 잔기와， 디안히드로핵시를을 포함한 디을 성분의 잔기를 포함하는 폴리에스테르 수지; 및 특정 조성의 충격 보강재를 포함하는 고분자 수지조성물로 안경테를 제조할 경우， 제조 공정 '면에세 사출성형 시 별도의 가공조제 또는 이형제 첨가가 불필요하고， 기존 안경테용 소재 대비 낮은 온도 (20 내지 60 °C )에서 가공이 가능하여 유틸리티 비용 절감이 가능하며， 사출 후 안정적 수축율로 급넁 단계가 감소하여 생산 효을성이 증가하는 장점이 았고, 아울러 강성， 내열성, 치수안정성， 및 내화학약품성이 우수하고， 특히 투명성이 우수하여 2차 가공 시 다양한
착색 및 필름 부착 등이 가능한 안경테를 제조할 수 있다는 점을 실험을 통하여 확인하고 발명을 완성하였다. The plastic material for the spectacle frame is not an environmentally friendly biomaterial, and has a problem of poor impact strength, poor transparency, and poor moldability. Accordingly, the present inventors are polyester resin comprising a residue of a dicarboxylic acid component including terephthalic acid and a residue of a dial component including dianhydronuclear; And when manufacturing a spectacle frame with a polymer resin composition containing a shock reinforcement of a specific composition, the manufacturing process ' no need to add a separate processing aid or release agent during the injection molding on the surface, lower temperature (20 to 60 than the conventional spectacle frame material It is possible to reduce the utility cost by processing at ° C), and it has the advantage of increasing the production efficiency by reducing the rapid stage with stable shrinkage rate after injection, and also has excellent rigidity, heat resistance, dimensional stability, and chemical resistance. ， Especially because of its high transparency, It was confirmed through experiments that the spectacle frame capable of coloring and film attachment, and completed the invention.
본 발명의 따른 안경테용 고분자 수지 조성물은， 테레프탈산을 포함한 디카르복실산 성분의 잔기와， 디안히드로핵시를을 포함한 디올 성분의 잔기를 포함하는 폴리에스테르 수지를 포함한다. The polymeric resin composition for eyeglass frames according to the present invention includes a polyester resin comprising a residue of a dicarboxylic acid component containing terephthalic acid and a residue of a diol component including dianhydronuclear.
본 명세서에서， '잔기 '는 특정한 화합물이 화학 반응에 참여하였을 때， 그 화학 반웅와 결과물에 포함되고 상기 특정 화합물로부터 유래한 일정한 부분 또는 단위를 의미한다. 예를 들어， 상기 디카르복실산 성분의 In the present specification, 'residue' means a certain part or unit included in the chemical reaction and the result and derived from the specific compound when the specific compound participates in the chemical reaction. For example, of the dicarboxylic acid component
'잔기 1 또는 디올 성분의 '잔기 1 각각은， 에스테르화 반응 또는 축중합 반응으로 형성되는 폴리에스테르에서 디카르복실산 성분으로부터 유래한 부분 또는 디올 성분으로부터 유래한 부분을 의미한다. Each of 'residue 1 ' or 'residue 1 ' of a diol component means a portion derived from a dicarboxylic acid component or a portion derived from a diol component in a polyester formed by an esterification reaction or a polycondensation reaction.
상기 '디카르복실산 성분'은 테레프탈산 등의 디카르복실산， 이의 알킬 에스테르 (모노메틸， 모노에틸， 디메틸， 디에틸 또는 디부틸에스테르 등 탄소수 1 내지 4의 저급 알킬 에스테르) 및 /또는 이들의 산무수물 (acid anhydr ide)을 포함하는 의미로 사용되며， 디을 성분과 반응하여， 테레프탈로일 부분 (terephthaloyl moi ety) 등의 디카르복실산 부분 (di carboxyl i c acidmoiety)을 형성할 수 있다. The 'dicarboxylic acid component' is a dicarboxylic acid such as terephthalic acid, an alkyl ester thereof (lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) and / or their It is used to include acid anhydrides, and may react with diol to form di carboxyl ic acid moiety such as terephthaloyl moiety.
상기 폴리에스테르 수지의 합성에 사용되는 디카르복실산 성분이 테레프탈산을 포함함에 따라, 제조되는 폴리에스테르 수지의 내열성， 내화학성 또는 내후성 (예를 들어， UV에 의한 분자량 감소 현상 또는 황변화 현상 방지) 등의 물성이 향상될 수 있다. As the dicarboxylic acid component used for synthesizing the polyester resin includes terephthalic acid, heat resistance, chemical resistance or weather resistance of the polyester resin produced (for example, prevention of molecular weight decrease or sulfur change due to UV) Physical properties such as can be improved.
상기 디카르복실산 성분은 기타의 디카르복실산 성분으로 방향족 디카르복실산 성분， 지방족 디카르복실산 성분 또는 이들의 흔합물을 더 포함할 수 있다. 이때 '기타의 디카르복실산 성분'은 상기 디카르복실산 성분 중 테레프탈산을 제외한 성분을 의미한다. The dicarboxylic acid component may further include an aromatic dicarboxylic acid component, an aliphatic dicarboxylic acid component, or a mixture thereof as other dicarboxylic acid components. In this case, 'other dicarboxylic acid component' means a component other than terephthalic acid among the dicarboxylic acid components.
' 한편， 상기 폴리에스테르 수지에 포함된 디카르복실산 성분은 탄소수 ' Meanwhile, the dicarboxylic acid component contained in the polyester resin has carbon number
8 내지 20의 방향족 디카르복실산 및 탄소수 4 내지 20의 지방족 디카르복실산으로 이루어진 군으로부터 선택되는 1종 이상을 더 포함할 수 있다. It may further include one or more selected from the group consisting of 8 to 20 aromatic dicarboxylic acid and aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
상기 방향족 디카르복실산 성분은 탄소수 8 내지 20， 바람직하게는
탄소수 8 내지 14의 방향족 디카르복실산 또는 이들의 흔합물 등일 수 있다. 상기 방향족 디카르복실산의 예로， 이소프탈산， 2，6-나프탈렌디카르복실산 등의 나프탈렌디카르복실산， 디페닐 디카르복실산， 4,4'- 스틸벤디카르복실산， 2,5-퓨란디카르복실산， 2,5-티오펜디카르복실산 등이 있으나 , 상기 방향족 디카르복실산의 구체적인 예가 이에 한정되는 것은 아니다. The aromatic dicarboxylic acid component is 8 to 20 carbon atoms, preferably Aromatic dicarboxylic acids having 8 to 14 carbon atoms, or a mixture thereof. Examples of the aromatic dicarboxylic acid include isophthalic acid, naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 4,4'- stilbendicarboxylic acid, 2, 5-furanedicarboxylic acid, 2,5-thiophene dicarboxylic acid, and the like, but specific examples of the aromatic dicarboxylic acid are not limited thereto.
상기 지방족 디카르복실산 성분은 탄소수 4 내지 20, 바람직하게는 탄소수 4 내지 12의 지방족 디카르복실산 성분 또는 이들의 흔합물 등일 수 있다. 상기 지방족 디카르복실산의 예로， 1,4-사이클로핵산디카르복실산， 1,3-사이클로핵산디카르복실산 등의 사이클로핵산디카르복실산， 프탈산， 세바식산， 숙신산， 이소데실숙신산， 말레산， 푸마르산， 아디픽산， 글루타릭산， 아젤라이산 등의 선형， 가지형 또는 고리형 지방족 디카르복실산 성분 등이 있으나， 상기 지방족 디카르복실산의 구체적인 예가 이에 한정되는 것은 아니다. The aliphatic dicarboxylic acid component may be an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms, or a mixture thereof. Examples of the aliphatic dicarboxylic acids include cyclonucleic acid dicarboxylic acids such as 1,4-cyclonucleic acid dicarboxylic acid, 1,3-cyclonucleic acid dicarboxylic acid, phthalic acid, sebacic acid, succinic acid, isodecyl succinic acid, Although there are linear, branched or cyclic aliphatic dicarboxylic acid components such as maleic acid, fumaric acid, adipic acid, glutaric acid, and azelaic acid, specific examples of the aliphatic dicarboxylic acid are not limited thereto.
한편， 상기 디카르복실산 성분은 테레프탈산 50 내지 100몰 ¾>, 바람직하게는 70 내지 100몰%； 및 방향족 디카르복실산 및 지방족 디카르복실산으로 이루어잔 군에서 선택된 1종 이상의 디카르복실산 0 내지 50몰%, 바람직하게는 0 내지 30몰¾>；를 포함할 수 있다. 상기 디카르복실산 성분 중 테레프탈산의 함량이 너무 작거나 너무 크면， 폴리에스테르 수지의 내열성， 내화학성 또는 내후성 등의 물성이 저하될 수 있다. . 한편， 상기 폴리에스테르 수지와 합성에 사용되는 디을 성분 (diol component)은 디안히드로핵시를 5 내지 60몰%， 사이클로핵산디메탄을.5 내지 80몰%, 및 잔량의 기타 디을 화합물을 포함할 수 있다. On the other hand, the dicarboxylic acid component is 50 to 100 mol ¾>, preferably 70 to 100 mol% of terephthalic acid; and at least one dicarboxyl selected from the group consisting of aromatic dicarboxylic acid and aliphatic dicarboxylic acid Acids 0-50 mol%, preferably 0-30 mol¾>; If the content of terephthalic acid in the dicarboxylic acid component is too small or too large, physical properties such as heat resistance, chemical resistance or weather resistance of the polyester resin may be lowered. . Meanwhile, the diol component used in the synthesis of the polyester resin may include 5 to 60 mol% of dianhydronuclear, 5 to 80 mol% of dimethyl methane, and the remaining amount of other diol compounds. Can be.
상기 디을 성분이 바람직하게는 디안히드로핵시를로써 아이소소바이드 (isosorbide, 1,4:3,6— dianhydroglucitol )를 포함함에 따라서， 제조되는 폴리에스테르 수지의 내열성이 향상될 뿐만 아니라 내화학성， 내약품성 등의 물성이 향상될 수 있다. 그리고， 상기 디을 성분 (diol component)에서 사이클로핵산디메탄올 (예를 들에 1,2- 사이클로핵산디메탄올， 1，3-사이클로핵산디메탄올 또는 1,4- 사이클로핵산디메탄올)의 함량이 증가할수록， 제조되는 폴리에스테르
수지의 내충격 강도가 크게 증가할 수 있다. As the diol component preferably includes isosorbide (1,4: 3,6—dianhydroglucitol) as dianhydronuclear, not only the heat resistance of the polyester resin produced is improved but also chemical resistance, Physical properties such as chemical properties may be improved. In addition, the content of cyclonucleodimethanol (for example, 1,2-cyclonucleodimethanol, 1,3-cyclonucleodimethanol or 1,4-cyclonucleodimethanol) increases in the diol component. Increasingly, the polyester produced The impact strength of the resin can be greatly increased.
또한， 상기 디올 성분은 상기 아이소소바이드 및 사이클로핵산디메탄을 이외로 기타의 디을 성분을 더 포함할 수 있다. 상기 '기타의 디올 성분'은 상기 아이소소바이드 및 사이클로핵산디메탄을 제외한 디올 성분을 의미하며, 예를 들어 지방족 디을， 방향족 디을 또는 이들의 흔합물일 수 있다. In addition, the diol component may further include other dial components in addition to the isosorbide and cyclonucleic acid dimethane. The 'other diol component' refers to a diol component other than the isosorbide and cyclonucleodimethane, and may be, for example, aliphatic di, aromatic di, or a combination thereof.
상기 폴리에스테르 수지에 포함된 디을 성분은 하기 화학식 1， 2 및 3으로 표시되는 화합물들로 이루어진 군으로부터 선택되는 1종 이상을 더 포함할 수 있다. The diol component included in the polyester resin may further include one or more selected from the group consisting of compounds represented by the following Chemical Formulas 1, 2 and 3.
[화학식 1] [Formula 1]
상기 화학식 1에서， ， ， 및 R4 는 각각 독립적으로 수소 또는 탄소수 1 내지 5 의 치환 또는 비치환된 알킬기이며， ηι 및 n2 는 각각 독립적으로 0 내지 3의 정수이고， In Formula 1 ,,, and R 4 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, ηι and n 2 are each independently an integer of 0 to 3,
2] 2]
상기 화학식 2에서， R5, ， R7 및 ¾는 각각 독립적으로 수소 또는 탄소수 1 내지 5 의 치환 또는 비치환된 얗킬기이며， In Formula 2, R 5 ,, R 7 and ¾ are each independently hydrogen or a substituted or unsubstituted white group having 1 to 5 carbon atoms,
[화학식 3]
상기 화학식 3에서, n은 1 내지 7의 정수이다. [Formula 3] In Formula 3, n is an integer of 1 to 7.
한편， 상기 폴리에스테르 수지는 디안히드로핵시를로 아이소소바이드 5 내지 60 몰 사이클로핵산디메탄을 5 내지 80 몰% 및 잔량의 기타 디올 화합물을 포함하는 디을 성분과 테레프탈산을 포함하는 디카르복실산 성분을 에스테르화 반웅시키는 단계; 상기' 에스테르화 반웅이 80% 이상 진행된 시점에 인계 안정제를 첨가하는 단계; 및 상기 에스테르화 반웅 생성물을 중축합 반웅시키는 단계를 포함하는 폴리에스테르 수지의 제조 방법에 의하여 제공될 수 있다. On the other hand, the polyester resin is a dicarboxylic acid containing a dial component and terephthalic acid containing 5 to 80 mol% of dianhydronucleoisoisosorbide 5 to 60 mol cyclohexamethane dimethane and a balance of other diol compounds Esterifying the components; Adding to the "phosphorus-containing stabilizer at the time of esterification is conducted banung than 80%; And it may be provided by a method for producing a polyester resin comprising the step of polycondensation reaction of the esterified reaction product.
이러한 폴리에스테르 수지의 제조 방법에 따라， 아연계 화합물을 포함하는 에스테르화 반웅 촉매를 사용하고, 상기 에스테르화 반응의 말기에， 예를 들어 반웅이 80% 이상 진행된 시점에서 반웅액에 인계 안정제를 첨가하고， 상기 에스테르화 반웅의 결과물을 중축합 시키면， 높은 내열성， 난연 특성 및 내충격성 등의 물성을 나타내며 우수한 외관 특성， 고투명도 및 우수한 성형 특성을 갖는 폴리에스테르 수지가 제공될 수 있다. 상기 테레프탈산을 포함하는 디카르복실산 성분, 사이클로핵산디메탄올， 아이소소바이드 및 기타 디올 화합물에 관한 구체적인 내용은 상술한 바와 같다. According to the method for producing a polyester resin, an esterification reaction catalyst containing a zinc-based compound is used, and at the end of the esterification reaction, for example, a phosphorus stabilizer is added to the reaction mixture at the time when reaction reaction proceeds by 80% or more. And, polycondensation of the result of the esterification reaction, it can be provided a polyester resin exhibiting physical properties such as high heat resistance, flame retardant properties and impact resistance having excellent appearance characteristics, high transparency and excellent molding properties. Details of the dicarboxylic acid component, cyclonucleic acid dimethanol, isosorbide and other diol compounds containing terephthalic acid are as described above.
상기 에스테르화 반웅 단계는 디카르복실산 성분 및 디올 성분을 0 내지 10.0 kg/crf 의 압력 및 150 내지 300 °C 은도에서 반웅시킴으로서 이루어질 수 있다. 상기 에스테르화 반웅 조건은 제조되는 폴리에스테르 수지의 구체적인 특성， 디카르복실산 성분과 글리콜의 몰비, 또는 공정 조건 등에 따라 적절하 조절될 수 있다. 구체적으로， 상기 에스테르화 반응 조건의 바람직한 예로, 0 내지 5.0kg/cin2 , 보다 바람직하게는 0. 1 내지 3.0 kg/ cm2 의 압력; 200 내지 270°C , 보다 바람직하게는 240 내지 260°C의 은도를 들 수 있다. The esterification reaction step may be accomplished by reacting the dicarboxylic acid component and the diol component at a pressure of 0 to 10.0 kg / crf and at 150 to 300 ° C. silver. The esterification reaction conditions can be appropriately adjusted according to the specific properties of the polyester resin to be produced, the molar ratio of the dicarboxylic acid component and glycol, or process conditions. Specifically, preferred examples of the esterification conditions, 0 to 5.0 kg / cin 2 , more preferably 0.1 to 3.0 kg / cm 2 pressure; 200 to 270 ° C., more preferably 240 to 260 ° C. may be mentioned.
그리고， 상기 에스테르화 반웅은 배치 (batch)식 또는 연속식으로 수행될 수 있고， 각각와 원료는 별도로 투입될 수 있으나, 디을 성분에
디카르복실산 성분을 흔합한 슬러리 형태로 투입하는 것이 바람직하다. 그리고， 상온에서 고형분인 디안히드로헥시를 등의 디올 성분은 물 또는 에틸렌글리콜에 용해시킨 후， 테레프탈산 등의 디카르복실산 성분에 흔합하여 슬러리로 만들 수 있다. 흑은 60oC 이상에서 디안히드로핵시를이 용융된 후， 테테프탈산 등의 디카르복실산 성분과 기타 디을 성분을 흔합하여 슬러리도 만들 수 있다. 또한， 디카르복실산 성분， 디안히드로핵시를 및 에틸렌글리콜 등의 공중합 디올 성분이 흔합된 슬러리에 물을 추가로 투입하여 슬러리의 유동성 증대에 도움을 줄 수도 있다. And, the esterification reaction can be carried out in a batch (batch) or continuous, each and the raw material may be added separately, but the diol component It is preferable to add the dicarboxylic acid component in the form of a mixed slurry. The diol component such as dianhydrohex, which is a solid content at room temperature, may be dissolved in water or ethylene glycol, and then mixed with a dicarboxylic acid component such as terephthalic acid to form a slurry. After the black melts the dianhydronuclears at 60 ° C. or higher, the slurry can also be prepared by mixing a dicarboxylic acid component such as tetephthalic acid and other dial components. In addition, water may be further added to a slurry in which a dicarboxylic acid component, a dianhydronucleic acid, and a copolymerized diol component such as ethylene glycol are mixed to help increase the fluidity of the slurry.
상기 에스테르화 반응에 참여하는 디카르복실산 성분과 디올 성분의 몰비는 1 : 1.05 내지 1 : 3.0 일 수 있다. 상기 디카르복실산 성분:디올 성분의 몰비가 1.05 미만이면， 중합반웅 시 미반응 디카르복실산 성분이 잔류하여 폴리에스테르 수지의 투명성이 저하될 수 있고， 상기 몰비가 3.0을 초과할 경우 중합반웅속도가 낮아지거나 수지의 생산성이 저하될 수 있다. The molar ratio of the dicarboxylic acid component and the diol component participating in the esterification reaction may be 1: 1.05 to 1: 3.0. When the molar ratio of the dicarboxylic acid component: diol component is less than 1.05, unreacted dicarboxylic acid component may remain during polymerization reaction, thereby decreasing transparency of the polyester resin, and when the molar ratio exceeds 3.0, polymerization reaction The speed may be lowered or the productivity of the resin may be lowered.
상기 에스테르화 반웅 생성물을 중축합 (poly-condensat ion) 반응시키는 단계는， 상기 디카르복실산 성분 및 디올 성분의 에스테르화 반응 생성물을 150 내지 300 °C 온도 및 600 내지 0.01 mmHg의 감압 조건에서 1 내지 24시간 동안 반웅시키는 단계를 포함할 수 있다. The poly-condensat ion reaction of the esterified reaction product may include reacting the esterification product of the dicarboxylic acid component and the diol component at 150 to 300 ° C. and a reduced pressure of 600 to 0.01 mmHg. And reacting for 24 hours.
이러한 중축합 반웅은， 150 내지 300 °C , 바람직하게는 200 내지Such polycondensation reaction is, 150 to 300 ° C, preferably 200 to
290 °C , 보다 바람직하게는 260 내지 280°C의 반응 온도; 및 600 내지 O . OlmmHg, 바람직하게는 200 내지 0.05 mmHg, 보다 바람직하게는 100 내지 0. 1 mmHg 의 감압 조건에서 수행될 수 있다. 상기 중축합 반웅의 감압 조건을 적용함에 따라서 중축합 반응의 부산물인 글리콜을 계외로 제거할 수 있으며， 이에 따라 상기 중축합 반웅이 600 내지 O . OlmmHg 감압 조건 범위를 벗어나는 경우 부산물의 제거가 불충분할 수 있다. A reaction temperature of 290 ° C., more preferably 260-280 ° C .; And 600 to O. OlmmHg, preferably from 200 to 0.05 mmHg, more preferably from 100 to 0.1 mmHg under reduced pressure conditions. By applying the decompression conditions of the polycondensation reaction reaction, glycol which is a by-product of the polycondensation reaction can be removed out of the system. Removal of by-products may be insufficient if out of OlmmHg decompression conditions.
또한， 상기 중축합 반웅이 150 내지 300°C 온도 범위 밖에서 일어나는 경우， 축중합 반웅이 150°C 이하로 진행되면 중축합 반응의 부산물인 글리콜을 효과적으로 계외로 제거하지 못해 최종 반웅 생성물의 고유 점도가 낮아 제조되는 폴리에스테르 수지의 물성이 저하될 수 있으며，
300 °C 이상으로 반응이 진행될 경우， 제조되는 폴리에스테르 수지의 외관이 황변 (yellowing)이 될 가능성이 높아진다. 그리고， 상기 중축합 반웅은 최종 반웅 생성물의 고유 점도가 적절한 수준에 이를 때까지 필요한 시간 동안， 예를 들면， 평균 체류 시간 1 내지 24시간 동안 진행될 수 있다. 한편， 상기 폴리에스테르 수지 조성물의 제조 방법은， 중축합 촉매를 추가로 첨가하는 단계를 더 포함할 수 있다. 이러한 중축합 촉매는， 상기 중축합 반웅의 개시 전에 에스테르화 반응 또는 에스테르 교환 반응의 생성물에 첨가될 수 있고， 상기 에스테르화 반응 ' 전에 디을 성분 및 디카르복실산 성분을 포함하는 흔합 슬러리 상에 첨가할 수 있으며， 상기 에스테르화 반웅 단계 도증에 첨가할 수도 있다. 、 In addition, when the polycondensation reaction occurs outside the temperature range of 150 to 300 ° C, if the condensation polymerization reaction proceeds below 150 ° C, the intrinsic viscosity of the final reaction product may not be effectively removed from the system as a glycol by-product of the polycondensation reaction Low physical properties of the polyester resin may be lowered, When the reaction proceeds to 300 ° C or more, the appearance of the polyester resin produced becomes more likely to be yellowing. The polycondensation reaction can then proceed for the required time until the intrinsic viscosity of the final reaction product reaches an appropriate level, for example for an average residence time of 1 to 24 hours. On the other hand, the production method of the polyester resin composition may further comprise the step of further adding a polycondensation catalyst. The polycondensation catalyst is added to the heunhap slurry containing dieul component and the dicarboxylic acid component the esterification may be added to the reaction, or the product of the transesterification, the esterification reaction "before prior to the start of the polycondensation banung It may be added to the esterification reaction step illustration. 、
상기■ 중축합 촉매로는, 티타늄계 화합물， 게르마늄계 화합물， 안티몬계 화합물， 알루미늄계 화합물， 주석계 화합물 또는 이들의 흔합물을 사용할 수 있다. 상기 티타늄계 화합물 및 게르마늄계 화합물의 예는 상술한 바와 같다. ■ in the polycondensation catalyst, it is possible to use a titanium compound, a germanium compound, an antimony compound, an aluminum-based compound, tin compound or a common compound. Examples of the titanium compound and the germanium compound are as described above.
한편， 상기 폴리에스테르 수지는， 유리전이은도가 115°C 내지 125°C, 또는 118 °C 내지 122°C이고 수평균분자량이 16,000 내지 26,000, 또는 20,000 내지 24,000， 또는 21,000 내지 23 ,000인 폴리에스테르 수지， 유리전이온도가 105°C 내지 115°C, 또는 108°C 내지 122°C이고 수평균분자량이 20， 000 내지 30,000， 또는 23,000 내지 26,000， 또는 23,500 내지 25， 500인 폴리에스테르 수지 또는 이들의 흔합물을 포함할 수 있다. On the other hand, the polyester resin, the glass transition degree is 115 ° C to 125 ° C, or 118 ° C to 122 ° C and the number average molecular weight of 16,000 to 26,000, or 20,000 to 24,000, or 21,000 to 23,000 Ester resin, polyester resin having a glass transition temperature of 105 ° C to 115 ° C, or 108 ° C to 122 ° C and a number average molecular weight of 20, 000 to 30,000, or 23,000 to 26,000, or 23,500 to 25, 500 or Combinations thereof.
구체적으로， 상기 폴리에스테르 수지로 유리전이온도가 115°C 내지 125°C이고 수평균분자량이 16,000 내지 26 ,000인 폴리에스테르 수지 및 유리전이온도가 105°C 내지 115°C이고 수평균분자량이 20,000 내지 30， 000인 폴리에스테르 수지의 흔합물을 사용하는 경우， 상기 유리전이온도가 115°C 내지 125°C이고 수평균분자량이 16,000 내지 26,000인 폴리에스테르 수지 및 유리전이온도가 105°C 내지 115°C이고 수평균분자량이 20,000 내지 30， 000인 폴리에스테르 수지의 중량비는 0.5:1 내지 5:1， 또는 0.5:1 내지 1:1， 또는 1:1 내지 3:1일 수 있다. Specifically, the polyester resin with a glass transition temperature of 115 ° C to 125 ° C and a number average molecular weight of 16,000 to 26,000 and a glass transition temperature of 105 ° C to 115 ° C and a number average molecular weight When using a mixture of polyester resin of 20,000 to 30,000, the glass transition temperature is 115 ° C to 125 ° C and the polyester resin and the glass transition temperature is 105 ° C to a number average molecular weight of 16,000 to 26,000 The weight ratio of the polyester resin having a 115 ° C. and a number average molecular weight of 20,000 to 30, 000 may be 0.5: 1 to 5: 1, or 0.5: 1 to 1: 1, or 1: 1 to 3: 1.
상기 유리전이온도가 115 °C 내지 125°C이고 수평균분자량이 16,000
내지 26, 000인 폴리에스테르 수지 및 유리전이온도가 105 °C 내지 115°C이고 수평균분자량이 20,000 내지 30 ,000인 폴리에스테르 수지가 상술한 특정 함량으로 포함되는 경우， 상기 안경테용 고분자 수지 조성물은 고투명성, 고강성， 고ᅫ열성 등의 향상된 특성을 가질 수 있다. 구체적으로， 상기 유리전이온도가 115°C 내지 125°C이고 수평균분자량이 16,000 내지 26, 000인 폴리에스테르 수지 및 유리전이온도가 105°C 내지 115°C이고 수평균분자량이 20,000 내지 30， 000인 폴리에스테르 수지의 중량비가 0.5:1미만이면， 상기 유리전이온도가 115 °C 내지 125°C이고 수평균분자량이 16,000 내지 26,000인 폴리에스테르 수지의 함량이 지나치게 감소하여， 상기 안경테용 고분자 수지 조성물의 내열성이 감소할 수 있다. 또한， 상기 유리전이온도가 115°C 내지 125°C이고 수평균분자량이 16,000 내지 26,000인 폴리에스테르 수지 및 유리전이은도가 105°C 내지 115°C이고 수평균분자량이 20,000 내지 30, 000인 폴리에스테르 수지의 증량비가 5:1초과이면， 유리전이온도가 105 °C 내지 115°C이고 수평균분자량이 20,000 내지 30 ,000인 폴리에스테르 수지의 함량이 지나치게 감소하여， 상기 안경테용 고분자 수지 조성물의 분자량이 감소할 수 있고， 이에 따라， 상기 안경테용 고분자 수지 조성물의 기계적 물성， 예를 들어 내층격성， 강성， 탄성률 등이 저하될 수 있다. The glass transition temperature is 115 ° C to 125 ° C and the number average molecular weight 16,000 When the polyester resin of 2 to 26, 000 and the polyester resin having a glass transition temperature of 105 ° C to 115 ° C and a number average molecular weight of 20,000 to 30,000 in the above-described specific content, the polymer resin composition for eyeglass frames May have improved properties such as high transparency, high stiffness, and high thermal conductivity. Specifically, the polyester resin having a glass transition temperature of 115 ° C to 125 ° C and a number average molecular weight of 16,000 to 26,000, and a glass transition temperature of 105 ° C to 115 ° C and a number average molecular weight of 20,000 to 30, When the weight ratio of the polyester resin of 000 is less than 0.5: 1, the glass transition temperature is 115 ° C to 125 ° C and the content of the polyester resin having a number average molecular weight of 16,000 to 26,000 is excessively reduced, the polymer resin for eyeglass frames The heat resistance of the composition may decrease. In addition, the polyester resin having a glass transition temperature of 115 ° C to 125 ° C and a number average molecular weight of 16,000 to 26,000, and a polyamide having a glass transition degree of 105 ° C to 115 ° C and a number average molecular weight of 20,000 to 30, 000 When the increase ratio of the ester resin is 5: 1, the content of the polyester resin having a glass transition temperature of 105 ° C to 115 ° C and a number average molecular weight of 20,000 to 30,000 is excessively reduced, so that the polymer resin composition for eyeglass frames Molecular weight may be reduced, and accordingly, mechanical properties of the polymer resin composition for eyeglass frames, for example, layer resistance, rigidity, elastic modulus, and the like may be reduced.
본 발명의 따른 안경테용 고분자 수지 조성물은， 부타디엔계 공중합체를 포함한 코어， 아크릴레이트 /방향족 비닐 공증합체를 포함한 내층 쉘 및 방향족 비닐계 고분자를 포함한 외층 쉘을 포함하는 충격 보강재；를 포함할 수 있다. The polymer resin composition for eyeglass frames according to the present invention may include an impact reinforcing material including a core including a butadiene copolymer, an inner layer shell including an acrylate / aromatic vinyl copolymer, and an outer layer shell containing an aromatic vinyl polymer; .
구체적으로, 전체 층격 보강재 100중량부 대비， 부타디엔계 공중합체를 포함한 코어 40 내지 90중량부， 아크릴레이트 /방향족 비닐 공중합체를 포함한 내층 쉘 5 내지 40중량부， 및 방향족 비닐계 공중합체를 포함한 외층 쉘 5 내지 20중량부를 포함하는 층격 보강재를 포함한다. 이들 범위를 벗어나면 충격 보강재로서 투명성과 내층격성의 밸런스가 무너질 수 있기 때문이다. Specifically, relative to 100 parts by weight of the total layered reinforcement, 40 to 90 parts by weight of the core including butadiene-based copolymer, 5 to 40 parts by weight of the inner layer shell including the acrylate / aromatic vinyl copolymer, and the outer layer including the aromatic vinyl copolymer A layer reinforcement comprising 5 to 20 parts by weight of shell. This is because the balance between the transparency and the layer resistance as the impact reinforcing material is out of these ranges.
본 발명에 따른 충격 보강재의 코어는 30 중량 % 내지 100 중량 %， 바람직하게는 40 중량 % 내지 90중량 %， 더욱 바람직하게는 50 증량 % 내지 80
중량 %의 부타디엔 단량체， 0 중량 % 내지 70 중량 %， 바람직하게는 10 중량 % 내지 60 중량 %， 더욱 바람직하게는 20 중량 % 내자 50 중량 %의 방향족 비닐 단량체， 0 중량 % 내지 10 중량 %의 이들과 공중합 가능한 비닐계 단량체, 0 중량 % 내지 5 중량 %의 가교성 단량체를 함유하는 단량체 흔합물을 중합하여 얻어지는 부타디엔계 공중합체를 포함할 수 있다. 부타디엔 단량체를 사용하는 것은 강도면에서 바람직하지만， 비정질 테레프탈산을 포함한 디카르복실산 성분의 잔기와， 디안히드로핵시를을 포함한 디올 성분의 잔기를 포함하는 폴리에스테르 수지의 굴절율과 떨어져 있기 때문에， 90 중량 % 이하로 하는 것이 투명성의 면에서 바람직하다. 또한， 40 중량 % 이상으로 함으로써 우수한 강도발현력이 얻어지므로 바람직하다. 더욱 바람직하게는 50 중량 % 내지 80 중량 %로 사용되는 것이 바람직하다. 방향족 비닐 단량체는 동일 분자내에 1개의 비닐성 이중결합과 1개 이상의 벤젠핵을 갖는 화합물로， 구체적으로는 스티렌， 알파-메틸스티렌， 2- 메틸스티렌， 3-메틸스티렌， 4-메틸스티렌， 4-에틸스티렌， 2， 5-디메틸스티렌 4-메특시스티렌， 4—에특시스티렌， 4-프로폭시스티렌， 4-부톡시스티렌， 클로로스티렌， 디클로로스티렌， 트리클로로스티렌， 비닐를루엔， 브로모스티렌， 디브로모스티렌， 트뫼브로모스티렌， 비닐나프탈렌， 이소프로페닐나프탈렌, 이소프로페닐비페닐， 디비닐밴젠과 같은 방향족 비닐 단량체 등을 들 수 있지만， 이들에 한정되는 것은 아니다. 이들을 사용하는 것은 고무입자의 굴절율을 높이고， 비정질 테레프탈산을 포함한 디카르복실산 성분의 잔기와， 디안히드로핵시를을 포함한 디올 성분의 잔기를 포함하는 폴리에스테르 수지의 굴절율에 접근시키는 점에서， 10 중량 % 이상， 또한 20 중량 % 이상 사용하는 것이 투명성의 면에서 바람직하고， 또 방향족 비닐 단량체를 60 중량 % 이하， 바람직하게는 50 증량 % 이하로 사용하는 것이 강도를 유지하기 때문에 바람직하다. 공중합가능한 비닐 단량체로는 (메타)아크릴산에스테르， 예컨대 (메타)아크릴산메틸, (메타)아크릴산에틸， (메타)아크릴산부틸 등의 탄소수 1-8 의 알코을의 (메타)아크릴산에스테르， (메타)아크릴로니트릴， (메타)아크릴산, (메타)아크릴산페닐， 비닐리덴시아나이트， 1 , 2- 디시아노에틸렌 등의 시안화 비닐화합물， 말레이미드계 화합물 등을 들 수
있지만， 이들에 한정되는 것은 아니다. 가교성 단량체로는， 예컨대 디메타아크릴산디비닐벤젠모노에틸렌글리콜， 디메타아크릴산에틸렌글리콜 등을 들 수 있지만， 이들에 한정되는 것은 아니다. 가교성 단량'체는 5 중량 %를 초과하여 사용하면 충격강도의 저하가 나타나기 때문에， 0 중량 % 내지 5 중량 %범위에서 사용하는 것이 바람직하다. The core of the impact modifier according to the invention is 30% to 100% by weight, preferably 40% to 90% by weight, more preferably 50% to 80% by weight. Wt% butadiene monomer, 0 wt% to 70 wt%, preferably 10 wt% to 60 wt%, more preferably 20 wt% to 50 wt% aromatic vinyl monomer, 0 wt% to 10 wt% And butadiene-based copolymers obtained by polymerizing a monomeric mixture containing a copolymerizable vinyl monomer and a monomer mixture containing 0 wt% to 5 wt% of a crosslinkable monomer. Although the use of butadiene monomers is preferable in terms of strength, it is separated from the refractive index of the polyester resin comprising residues of dicarboxylic acid components including amorphous terephthalic acid and residues of diol components including dianhydronuclear. It is preferable to set it as weight% or less from a transparency point. Moreover, since it is possible to obtain excellent strength expression power by setting it to 40 weight% or more, it is preferable. More preferably, it is used at 50% by weight to 80% by weight. Aromatic vinyl monomers are compounds having one vinyl double bond and one or more benzene nuclei in the same molecule, specifically styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4 -Ethyl styrene, 2, 5-dimethyl styrene 4-methoxy styrene, 4-especial styrene, 4-propoxy styrene, 4-butoxy styrene, chloro styrene, dichloro styrene, trichloro styrene, vinylluene, bromostyrene And aromatic vinyl monomers such as dibromostyrene, tmobromostyrene, vinyl naphthalene, isopropenyl naphthalene, isopropenyl biphenyl, divinylvangen, and the like, but are not limited thereto. Using them increases the refractive index of the rubber particles and approaches the refractive index of the polyester resin including residues of the dicarboxylic acid component including amorphous terephthalic acid and residues of the diol component including dianhydronuclear. It is preferable to use at least 20% by weight or more, and in terms of transparency, and to use the aromatic vinyl monomer at 60% by weight or less, preferably 50% by weight or less, since the strength is maintained. Examples of vinyl monomers copolymerizable include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate. Vinyl cyanide compounds such as nitrile, (meth) acrylic acid, phenyl (meth) acrylate, vinylidene cyanide, 1,2-dicyanoethylene, maleimide compounds, and the like. However, it is not limited to these. Examples of the crosslinkable monomer include divinyl acrylate divinylbenzene monoethylene glycol, dimethacrylate ethylene glycol, and the like, but are not limited thereto. Crosslinkable monomer ' sieve is used in the range of 0% by weight to 5% by weight because the impact strength is lowered when used in excess of 5% by weight.
본 발명에 따른 층격 보강재의 내층 쉘은 60 중량 % 내지 98 중량 %， 바람직하게는 65 중량 % 내지 95 중량 % 의 방향족 비닐 단량체， 2 중량 ¾； 내지 40 중량 %， 바람직하게는 5 증량 % 내지 35 중량 %의 히드록실기 또는 알콕시기를 함유하는 (메타)아크릴산에스테르를 함유하는 단량체， 0 증량 % 내지 20 중량 % 의 이들과 공중합가능한 비닐계 단량체를 함유하는 단량체 흔합물을 증합하여 얻어지는 아크릴레이트 /방향족 비닐 공중합체를 포함할 수 있다. The inner shell of the layered reinforcement according to the present invention is 60% to 98% by weight, preferably 65% to 95% by weight of an aromatic vinyl monomer, 2% by weight; to 40% by weight, preferably 5% by weight to 35%. Acrylate / aromatic obtained by combining a monomer containing a (meth) acrylic acid ester containing a weight percent hydroxyl group or an alkoxy group, and a monomer mixture containing 0 weight percent to 20 weight percent vinyl monomer copolymerizable with these. Vinyl copolymers.
본 명세서에서， '아크릴레이트 /방향족 비닐 공중합체'는 아크릴레이트 단량체와 방향족 비닐 단량체의 흔합물을 중합하여 얻어지는 공중합체를 의미한다. In the present specification, 'acrylate / aromatic vinyl copolymer' means a copolymer obtained by polymerizing a mixture of an acrylate monomer and an aromatic vinyl monomer.
상기 내층 쉘을 중합하여 만드는 단량체 흔합물의 주입방법 등에 특별히 제한은 없고， 연속일단추가， 이단추가 등의 방법이 이용된다. 내층 쉘을 형성하는 방향족 비닐 단량체는 동일 분자내에 1개의 비닐성 이중결합과 1개 이상의 벤젠핵을 갖는 화합물로， 구체적으로는 스티렌， α- 메틸스티렌， 2-메틸스티렌, 3-메틸스티렌, 4-메틸스티렌， 4-에틸스티렌， 2 , 5—디메틸스티렌， 4-메록시스티렌， 4-에특시스티렌， 4ᅳ프로폭시스티렌， 4- 부톡시스티렌, 클로로스티렌， 디클로로스티렌， 트리클로로스티렌， 비닐를루엔， 브로모스티렌， 디브로모스티렌， 트리브로모스티렌， 비닐나프탈렌, 이소프로페닐나프탈렌, 이소프로페닐비페닐과 같은 방향족 비닐 단량체류 등을 들 수 있지만 이들에 한정되는 것은 아니다. 이들을 사용하는 것은 쉘의 굴절율을 높이고， 비정질 테레프탈산을 포함한 디카르복실산 성분의 잔기와， 디안히드로핵시를을 포함한 디올 성분의 잔기를 포함하는 폴리에스테르 수지의 굴절율에 접근시키기 때문에， 투명성의 면에서 바람직하다. 히드록실기 또는 알콕시기를 함유하는 (메타)아크릴산에스테르를 함유하는 단량체는 히드록시에틸아크릴레이트,
히드록시프로필아크릴레이트 히드록시아크릴레이트 히드록시에틸메타아크릴레이트, 히드록시프로필메타아크릴레이트 등의 히드록시메타아크릴레이트， 메특시에틸아크릴레이트， 에특시에틸아크릴레이트 등의 알콕시아크릴레이트， 메특시에틸메타아크릴레이트 에록시에틸메타아크릴레이트 등의 알콕시메타아크릴레이트 등을 들 수 있지만， 이들에 한정되는 것은 아니다. 이들을 내층 쉘에 사용하는 것은， 비정질 테레프탈산을 포함한 다카르복실산 성분의 잔기와 디안히드로핵시를을 포함한 디을 성분의 잔기를 포함하는 폴리에스테르 수지와， 코어쉘 개질제의 계면접착성을 양호하게 하기 때문에 바람직하다. 또한， 용융흔합시의 점도도 높게 하지 않기 때문에 바람직하다. 공중합 가능한 비닐 단량체로는 (메타)아크릴산에스테르， 예컨대 (메타)아크릴산메틸， (메타)아크릴산에틸，There is no restriction | limiting in particular in the injection method of the monomer mixture formed by superposing | polymerizing the said inner layer shell, The methods, such as a continuous single addition and a two-stage addition, are used. The aromatic vinyl monomer forming the inner shell is a compound having one vinyl double bond and at least one benzene nucleus in the same molecule, specifically styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4 -Methyl styrene, 4-ethyl styrene, 2, 5- dimethyl styrene, 4- methoxy styrene, 4- ethoxy styrene, 4 ᅳ propoxy styrene, 4- butoxy styrene, chloro styrene, dichloro styrene, trichloro styrene, Aromatic vinyl monomers such as vinylluene, bromostyrene, dibromostyrene, tribromostyrene, vinylnaphthalene, isopropenyl naphthalene, isopropenyl biphenyl, and the like. Using them increases the refractive index of the shell and approaches the refractive index of the polyester resin containing residues of the dicarboxylic acid component including amorphous terephthalic acid and residues of the diol component including dianhydronuclear acid. Preferred at Monomers containing a (meth) acrylic acid ester containing a hydroxyl group or an alkoxy group include hydroxyethyl acrylate, Hydroxypropyl acrylate, alkoxy acrylate such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, methoxyethyl acrylate, ecoxyethyl acrylate, etc. Although alkoxy methacrylates, such as methacrylate hydroxyethyl methacrylate, etc. are mentioned, It is not limited to these. The use of these in the inner layer shell improves the interfacial adhesion between the polyester resin containing the residue of the polycarboxylic acid component including amorphous terephthalic acid and the residue of the dial component including dianhydronuclear, and the core shell modifier. desirable. Moreover, since the viscosity at the time of melt mixing does not become high, it is preferable. Examples of vinyl monomers copolymerizable include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate,
(메타)아크릴산부틸 등의 탄소수 1 내지 8 의 알코올의Of alcohols having 1 to 8 carbon atoms such as butyl (meth) acrylate
(메타)아크릴산에스테르， (메타)아크릴로니트릴， (메타)아크릴산, (메타)아크릴산페닐, 비닐리덴시아네이트, 1 , 2-디시아노에틸렌 등의 시안화비닐화합물， 말레이미드계 화합물 등을 들 수 있지만， 이들에 한정되는 것은 아니다. (Meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylic acid, (meth) acrylic acid phenyl, vinylidene cyanate, vinyl cyanide compounds, such as 1 and 2-dicyanoethylene, maleimide type compounds, etc. are mentioned. However, it is not limited to these.
본 발명에 따른 층격 보강재에 사용되는 외층 쉘은 방향족 비닐 단량체 10 중량 % 내지 100 중량 %， 알킬 (메타)아크릴레이트 0 중량 % 내지 90 증량 %; 공중합가능한 비닐계 단량체 0 중량 % 내지 50 중량 %를 함유하는 단량체 흔합물을 중합하여 얻어지는 방향족 비닐계 고분자를 포함할 수 있다. 외층 쉘을 중합하여 만드는 단량체 흔합물의 주입방법 등에 특별히 제한은 없고， 연속일단추가， 이단추가 등의 방법이 이용된다. 외층 쉘을 형성하는 알킬 (메타)아크릴레이트에서 상기 알킬기는 탄소수 1 내지 8 의 직쇄 또는 분지쇄의 알킬기를 포함할 수 있고, 상기 알킬 (메타)아크릴레이트로는 아크릴산 또는 메타크릴산의 에스테르화합물， 예컨대 메타크릴산메틸， 메타아크릴산에틸， 메타아크릴산부틸， 아크릴산메틸， 아크릴산에틸， 아크릴산부틸 등을 들 수 있지만 이들에 한정되는 것은 아니다. 이들을 사용하는 것은， 비정질 테레프탈산을 포함한 디카르복실산 성분의 잔기와 디안히드로핵시를을 포함한 디올 성분의
잔기를 포함하는 폴리에스테르 수지와의 분산성을 양호하게 하기 때문에 바람직하다. 방향족 비닐 단량체는 예컨대 스티렌， α-메틸스티렌， 2- 메틸스티렌 3-메틸스티렌， 4-메틸스티렌， 4-에틸스티렌， 2， 5-디메틸스티렌， 4-메톡시스티렌， 4-에특시스티렌， 4-프로폭시스티렌， 4-부록시스티렌, 클로로스티렌， 디클로로스티렌， 트리클로로스티렌， 비닐를루엔, 브로모스티렌， 디브로모스티렌， 트리브로모스티렌， 비닐나프탈렌， 이소프로페닐나프탈렌， 이소프로페닐비페닐과 같은 방향족 비닐 단량체류 등을 들 수 있지만 이들에 한정되는 것은 아니다. 이들을 사용하는 것은 쉘의 굴절율을 높이고 비정질 테레프탈산을 포함한 디카르복실산 성분의 잔기와 디안히드로핵시를을 포함한 디을 성분의 잔기를 포함하는 폴리에스테르 수지의 굴절율에 접근시키기 때문에， 투명성의 면에서 바람직하다. 공중합 가능한 단량체로는 아크릴산, 메타아크릴산， 메타아크릴로니트릴， 아크릴로니트릴， 비닐리덴시아네이트， 1，2- 디시아노에틸렌 등의 시안화 비닐화합물， 말레이미드계 화합물 등을 들 수 있지만， 이들에 한정되는 것은 아니다. 층격 보강재에 내층 쉘， 외층 쉘을 형성하는 것은， 내층 쉘은 층격 보강재의 굴절율을， 비정질 테레프탈산을 포함한 디카르복실산 성분의 잔기와 디안히드로핵시를을 포함한 디을 성분의 잔기를 포함하는 폴리에스테르 수지의 굴절율에 접근시키는 것은, 비정질 테레프탈산을 포함한 디카르복실산 성분의 잔기와 디안히드로핵시를을 포함한 디올 성분의 잔기를 포함하는 폴리에스테르 수지와， 코어쉘 개질제의 계면접착성을 양호하게 하기 위해서 이고， 외층 쉘은 층격 보강재의 비정질 테레프탈산을 포함한 디카르복실산 성분의 잔기와， 디안히드로핵시를을 포함한 디을 성분의 잔기를 포함하는 폴리에스테르 수지에 대한 분산성을 높이는 역할을 부여하기 위해서이다. 한편, 층격 보강재의 입자직경은 특별히 제한은 없지만， 0.0 /m 이상이면 충격강도의 향상의 정도가 크고, 0.5/im 아하이면 투명성이 확보되기 때문에， 0.05 내지 0. 皿 인 것이 바람직하다. 상기 부타디엔계 공중합체의 입자직경을 조제하는 방법으로는 일본 특허공보 소 43-12158에 개시된 수용성 전해질을 사용하여 그래프트중합 중에 웅집비대 시키는 방법， 또는 일본 공개특허공보 평 8— 012704에 개시되어 있는 바와 같은
(메타)아크릴산에스테르와 불포화산의 공중합체로 이루어지는 산기 함유 라텍스를 사용하는 방법도 이용할 수 있다. The outer shell used for the layered reinforcement according to the present invention comprises 10% to 100% by weight of aromatic vinyl monomer, 0% to 90% by weight of alkyl (meth) acrylate; An aromatic vinyl polymer obtained by polymerizing a monomer mixture containing 0 wt% to 50 wt% of a copolymerizable vinyl monomer may be included. There is no restriction | limiting in particular in the injection method of the monomer mixture formed by superposing | polymerizing an outer shell, and methods, such as a continuous single addition and a two-stage addition, are used. In the alkyl (meth) acrylate forming the outer shell, the alkyl group may include a linear or branched alkyl group having 1 to 8 carbon atoms, and the alkyl (meth) acrylate may be an ester compound of acrylic acid or methacrylic acid, Examples include, but are not limited to, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and the like. The use of these is based on the residues of the dicarboxylic acid component containing amorphous terephthalic acid and the diol component containing dianhydronuclear. It is preferable because it makes the dispersibility with the polyester resin containing a residue favorable. Aromatic vinyl monomers include, for example, styrene, α-methylstyrene, 2-methylstyrene 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 2, 5-dimethylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4-propoxystyrene, 4-butoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, vinylluene, bromostyrene, dibromostyrene, tribromostyrene, vinylnaphthalene, isopropenyl naphthalene, isopropenyl Aromatic vinyl monomers, such as biphenyl, etc. are mentioned, It is not limited to these. The use of these is preferable in terms of transparency because it increases the refractive index of the shell and approaches the refractive index of the polyester resin containing the residue of the dicarboxylic acid component including amorphous terephthalic acid and the dial component including dianhydronuclear. Do. Examples of the copolymerizable monomer include acrylic acid, methacrylic acid, methacrylonitrile, acrylonitrile, vinylidecyanate, vinyl cyanide compounds such as 1,2-dicyanoethylene, maleimide compounds, and the like. It doesn't happen. Forming the inner shell and outer shell in the laminar reinforcement, the inner shell is the polyester containing the residues of the dicarboxylic acid component including dianhydronuclear and the residues of the dicarboxylic acid component including amorphous terephthalic acid Approaching the refractive index of the resin is to improve the interfacial adhesion between the polyester resin comprising the residue of the dicarboxylic acid component containing amorphous terephthalic acid and the residue of the diol component including dianhydronuclear, and the core shell modifier. In order to provide a role of increasing the dispersibility of a polyester resin containing a residue of a dicarboxylic acid component including amorphous terephthalic acid of a lamella reinforcement and a dial component containing a dianhydronucleic acid of the layer reinforcing material to be. On the other hand, the particle diameter of the layered reinforcing material is not particularly limited, but the degree of improvement of the impact strength is large at 0.0 / m or more, and transparency is secured at 0.5 / im or less, so it is preferably 0.05 to 0.0 m. As a method for preparing the particle diameter of the butadiene-based copolymer, a method of increasing the size during graft polymerization using a water-soluble electrolyte disclosed in Japanese Patent Publication No. 43-12158, or as disclosed in JP-A-8-012704 same The method of using the acidic radical containing latex which consists of a copolymer of (meth) acrylic acid ester and unsaturated acid can also be used.
또한， 상기 층격 보강재에 포함된 코어의 입자 직경은 특별히 제한은 없지만， 0.05/ 이상이면 충격강도의 향상의 정도가 크고， 0. 1 이하이면 투명성이 확보되기 때문에， 0.05， 내지 0. 1 ， 또는 0.06 내지 0.08/im 인 것이 바람직하다. In addition, the particle diameter of the core included in the layered reinforcing material is not particularly limited, but if it is 0.05 / or more, the degree of improvement in impact strength is large, and if it is 0.01 or less, transparency is ensured, 0.05, to 0.1, or It is preferable that it is 0.06-0.08 / im.
본 발명에 따른 충격 보강재는 유화중합， 현탁중합， 용액중합 등에서 얻을 수 있지만 유화중합이 바람직하다. 유화중합에 대해서는 공지된 유화방법, 중합순서에 의해 제조된다. The impact reinforcing material according to the present invention can be obtained in emulsion polymerization, suspension polymerization, solution polymerization, etc., but emulsion polymerization is preferred. The emulsion polymerization is produced by a known emulsion method or polymerization procedure.
또한， 상기 충격 보강재의 함량이 전체 안경테용 고분자 수지 조성물 함량에 대하여 1 중량 % 내지 20 중량 %일， 또는 5 중량 % 내지 15 중량 %， 또는 8 중량 % 내지 12 중량 %일 수 있다. 상기 층격 보강재의 함량이 1증량 % 미만이면， 상기 충격 보강재에 의한 내층격성 향상 효과가 감소할 수 있고， 또한， 상기 층격 보강재의 함량이 20중량 % 초과이면， 투명성이 감소하여 다양한 색발현에 대한 착색성이 저하될 수 있는 문제점이 발생할 수 있다. 본 발명의 또 다른 측면에 따르면 상기 안경테용 수지 조성물의 성형품을 포함하는 안경테가 제공될 수 있다. 상기 안경테는 상기 안경테용 수지 조성물을 성형하여 제조되는 성형품을 포함할 수 있다. 상기 성형품은 그 적용 용도에 따라서 상기 안경테용 수지 조성물을 다양한 성형 방법， 예를 들어 사출, 압출， 압출 블로우， 사출 블로우 및 프로파일 압출 등의 성형공정 및 이를 이용한 열성형 공정과 같은 후가공 등의 방법을 통하여 성형함으로서 얻을 수 있다. In addition, the content of the impact reinforcing material may be 1% by weight to 20% by weight, or 5% by weight to 15% by weight, or 8% by weight to 12% by weight with respect to the total content of the polymer resin composition for eyeglass frames. When the content of the layered reinforcing material is less than 1% by weight, the effect of improving the layered resistance by the impact reinforcing material may be reduced. Also, when the content of the layered reinforcing material is more than 20% by weight, transparency may be reduced to various colors. Problems may occur that the colorability may be lowered. According to another aspect of the present invention may be provided with a spectacle frame including a molded article of the resin composition for the spectacle frame. The spectacle frame may include a molded article manufactured by molding the resin composition for the spectacle frame. According to the application, the molded article may be formed using various molding methods such as injection molding, extrusion, extrusion blow, injection blow, profile extrusion, and post-processing such as thermoforming using the same. It can be obtained by molding through.
상기 성형품의 구체적인 형상이나 크기는 그 적용 용도에 따라서 다양하게 결정될 수 있으며， 그 예가 특별하게 한정되지 않는다. Specific shape or size of the molded article can be determined in various ways depending on the application, the example is not particularly limited.
상기 안경테는 상기 안경테용 수지 조성물의 성형품과 함께 금속 , 안료 등을 더 포함할 수 있다. 상기 금속 또는 안료는 안경테 제조 분야에서 통상적으로 널리 사용되는 것이면 제한 없이 사용할 수 있으며， 그 예가 특별하게 한정되지 않는다.
이하， 본 발명의 바람직한 실시예를 상세히 설명하기로 한다. 다만, 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지는 않는다 할 것이다 실시예 1 The spectacle frame may further include a metal, a pigment, and the like together with the molded article of the resin composition for the spectacle frame. The metal or pigment may be used without limitation as long as it is commonly used in the field of eyeglass frame manufacturing, and examples thereof are not particularly limited. Hereinafter, preferred embodiments of the present invention will be described in detail. However, these Examples are only for illustrating the present invention, and the scope of the present invention is not to be construed as being limited by these Examples. Example 1
이축흔련압출기 (Φ : 40mm , L/D = 40)를 사용하여 사용하여 테레프탈산 -아이소소바이드 -1， 4ᅳ사이클로핵산디을-에틸렌글리콜 공중합 폴리에스테르 수지 (Tg ： 120 °C , 수평균분자량 ： 2.2만) 60중량 %， 테레프탈산-아이소소바이드 -1 , 4-사이클로핵산디올-에틸렌글리콜 공중합 폴리에스테르 수지 (Tg ： 110 °C , 수평균분자량 ： 2.4만) 30중량 %, 및 메틸메타크릴레이트 -부타디엔-스티렌 그라프트 공중합체 10중량 %로 이루어진 수지 100중량 %에 대해 아크릴로니트릴 -스티렌-글리시딜 메타크릴레이트 0.5중량%， 페놀계 1차 산화안정제， 포스파이트계 2차 산화안정제를 각각 0.2중량 % 첨가하여， 균일하게 흔련 압출을 진행하고 펠렛을 제조하였다. Terephthalic acid-isosorbide-1, 4 디 cyclonucleic acid di-ethylene glycol copolymerized polyester resin (Tg: 120 ° C, number average molecular weight :) using a biaxial kneading extruder (Φ: 40 mm, L / D = 40) 2.20,000) 60% by weight, terephthalic acid-isobide-1, 4-cyclonucleodiol diol-ethylene glycol copolyester polyester resin (Tg: 110 ° C, number average molecular weight: 2.40,000) 30% by weight, and methyl methacrylate -0.5% by weight of acrylonitrile-styrene-glycidyl methacrylate, phenolic primary oxidative stabilizer, phosphite secondary oxidative stabilizer to 100% by weight of resin consisting of 10% by weight of butadiene-styrene graft copolymer 0.2 wt% of each was added to uniformly extrude the mixture to prepare pellets.
상기에서， 테레프탈산-아이소소바이드 -1 , 4-사이클로핵산디올- 에틸렌글리콜 공중합 폴리에스테르 수지는 국내 에스케이케미칼사의 고충격 친환경수지인 에코젠 (EC0ZEN) , 메틸메타크릴레이트 -부타디엔-스티렌 그라프트 공중합체는 일본 KANEKA사의 코어-쉘 고무 (Core-She 1 1 Rubber )형태의 그라프트 MBS 제품인 M-300 , 아크릴로니트릴 -스티렌- 글리시딜 메타크릴레이트는 중국 SUNNY FC사의 SAG-005 , 페놀계 1차 산화안정제는 일본 ADEKA사의 Α0-60 , 포스파이트계 2차 산화안정제는 스위스 Cl ar i ant사의 Igar fos 168 제품을 사용하였다. 실시예 2 In the above, terephthalic acid-isosorbide-1, 4-cyclonucleodiol diol-ethylene glycol copolymerized polyester resin is eco-enzyme (EC0ZEN), methyl methacrylate-butadiene-styrene graft air M-300, acrylonitrile-styrene-glycidyl methacrylate, a graft MBS product in the form of a core-shell rubber (Core-She 11 1 Rubber) manufactured by KANEKA, Japan, is SAG-005, a phenolic system of SUNNY FC of China. As the primary oxidative stabilizer, AADEO 60 from ADEKA, Japan, and the phosphite secondary oxidative stabilizer were used as Igar fos 168 from Cl ar i ant, Switzerland. Example 2
이축흔련압출기 (Φ : 40mm , L/D = 40)를 사용하여 사용하여 테레프탈산 -아이소소바이드 -1， 4-사이클로핵산디올-에틸렌글리콜 공중합 폴리에스테르 수지 (Tg ： 120 °C , 수평균분자량 ： 2.2만) 50중량 %， 테레프탈산 -아이소소바이드 -1 , 4-사이클로핵산디을-에틸렌글리콜 공중합 폴리에스테르 수지 (Tg ： 110 °C , 수평균분자량 ： 2.4만) 40중량 %， 및
메틸메타크릴레이트 -부타디엔-스티렌 그라프트 공중합체 10중량 %로 이루어진 수지 100중량 %에 대해 아크릴로니트릴 -스티렌-글리시딜 메타크릴레이트 0.5중량%， 페놀계 1차 산화안정제， 포스파이트계 2차 산화안정제를 각각 0.2중량 % 첨가하여， 균일하게 흔련 압출을 진행하고 펠뻣을 제조하였다. Terephthalic Acid-Isosorbide-1, 4-cyclonucleic acid diol-ethylene glycol Copolymerized Polyester Resin (Tg: 120 ° C, Number Average Molecular Weight) by using a twin screw extruder (Φ: 40mm, L / D = 40) 2.2 million) 50% by weight, terephthalic acid-iso carbide -1, 4-cyclodiacid di-ethylene glycol copolymerized polyester resin (Tg: 110 ° C, number average molecular weight: 2.4 million) 40 weight percent, and 0.5% by weight of acrylonitrile-styrene-glycidyl methacrylate, 100% by weight of phenol-based primary oxidation stabilizer, phosphite based on 100% by weight of resin consisting of 10% by weight of methyl methacrylate-butadiene-styrene graft copolymer 0.2 wt% of the primary oxidative stabilizer was added to each other to uniformly extrude the mixture to prepare a stiff.
상기에서， 테레프탈산-아이소소바이드 -1， 4-사이클로핵산디을- 에틸렌글리콜 공중합 폴리에스테르 수지는 국내 에스케이케미칼사의 고충격 친환경수지인 에코젠 (EC0ZEN) , 메틸메타크릴레이트 -부타디엔-스티렌 그라프트 공중합체는 일본 KANEKA사의 코어-쉘 고무 (Core-Shel l Rubber )형태의 그라프트 MBS 제품인 M-300 , 아크릴로니트릴 -스티렌- 글리시딜 메타크릴레이트는 중국 SUNNY FC사의 SAG-005 , 페놀계 1차 산화안정제는 일본 ADEKA사의 AO-60 , 포스파이트계 2차 산화안정제는 스위스 Cl ar i ant사의 Igarfos 168 제품을 사용하였다. 실시예 3 In the above, terephthalic acid-isosorbide-1, 4-cyclonucleic acid di- ethylene glycol copolymerized polyester resin is Eco-Zen (EC0ZEN), methyl methacrylate-butadiene-styrene graft air M-300, acrylonitrile-styrene-glycidyl methacrylate, a graft MBS product in the form of a core-shell rubber of KANEKA, Japan, is SAG-005, phenolic 1, manufactured by SUNNY FC of China. The primary oxidative stabilizer was AO-60 from ADEKA, Japan, and the phosphite-based secondary oxidative stabilizer was from Igarfos 168 from Cl ar i ant, Switzerland. Example 3
이축흔련압출기 (Φ : 40mm , L/D = 40)를 사용하여 사용하여 테레프탈산 -아이소소바이드 -1， 4-사이클로핵산디올-에틸렌글리콜 공중합 폴리에스테르 수지 (Tg ： 120 °C , 수평균분자량 ： 2.2만) 45중량 %， 테레프탈산 -아이소소바이드 -1， 4-사이클로핵산디을-에틸렌글리콜 공중합 폴리에스테르 수지 (Tg ： 110 °C , 수평균분자량 ： 2.4만) 45중량 %， 및 메틸메타크릴레이트 -부타디엔-스티렌 그라프트 공중합체 10중량 %로 이루어진 수지 100중량 %에 대해 아크릴로니트릴 -스티렌-글리시딜 메타크릴레이트 0.5중량 %， 페놀계 1차 산화안정제， 포스파이트계 2차 산화안정제를 각각 0.2중량 % 첨가하여， 균일하게 흔련 압출을 진행하고 펠렛을 제조하였다. Terephthalic Acid-Isosorbide-1, 4-cyclonucleic acid diol-ethylene glycol Copolymerized Polyester Resin (Tg: 120 ° C, Number Average Molecular Weight) by using a twin screw extruder (Φ: 40mm, L / D = 40) 2.2 million) 45 weight%, terephthalic acid-iso carbide -1, 4-cyclodifluorodi- ethylene glycol copolymerized polyester resin (Tg: 110 ° C, number average molecular weight: 2.4 million) 45 weight%, and methyl methacrylate 0.5% by weight of acrylonitrile-styrene-glycidyl methacrylate, phenolic primary oxidative stabilizer, phosphite secondary oxidative stabilizer to 100% by weight of resin consisting of 10% by weight of butadiene-styrene graft copolymer 0.2 wt% of each was added to uniformly extrude the mixture to prepare pellets.
상기에서， 테레프탈산-아이소소바이드 -1 ,4-사이클로핵산디을- 에틸렌글리콜 공중합 폴리에스테르 수지는 국내 에스케이케미칼사의 고충격 친환경수지인 에코젠 (EC0ZEN) , 메틸메타크릴레이트 -부타디엔-스티렌 그라프트 공중합체는 일본 KANEKA사의 코어-쉘 고무 (Core-Shel l Rubber )형태의 그라프트 MBS 쎄품인 M-300 , 아크릴로니트릴 -스티렌-
글리시딜 메타크릴레이트는 중국 . SUNNY FC사의 SAG-005 , 페놀계 1차 산화안정제는 일본 ADEKA사의 A0-60 , 포스파이트계 2차 산화안점제는 스위스 Cl ar i ant사의 Igarfos 168 제품을 사용하였다. 실시예 4 In the above, terephthalic acid-isosorbide-1,4-cyclonucleic acid di- ethylene glycol copolymerized polyester resin is Eco-Zen (EC0ZEN), methyl methacrylate-butadiene-styrene graft air The coalescing is made of M-300, acrylonitrile-styrene, a graft MBS product in the form of core-shell rubber (KANEKA, Japan). Glycidyl methacrylate is China. SAG-005 from SUNNY FC, A0-60 from ADEKA of Japan, and phosphite-based second oxidation stabilizer from Igarfos 168 from Cl ar iant, Switzerland, were used. Example 4
이축흔련압출기 (Φ : 40mm , L/D = 40)를 사용하여 사용하여 테레프탈산 -아이소소바이드ᅳ 1， 4—사이클로핵산디을-에틸렌글리콜 공중합 폴리에스테르 수지 (Tg ： 120 °C , 수평균분자량 ： 2.2만) 60중량 %， 테레프탈산 -아이소소바이드 -1， 4-사이클로핵산디올-에틸렌글리콜 공중합 폴리에스테르 수지 ( ： 110 °C , 수평균분자량 ： 2.5만) 30중량 %， 및 메틸메타크릴레이트 -부타디엔-스티렌 그라프트 공중합체 10중량 %로 이루어진 수지 100중량 %에 대해 아크릴로니트릴 -스티렌-글리시딜 메타크릴레이트 0.5중량%， 페놀계 1차 산화안정제， 포스파이트계 2차 산화안정제를 각각 0.2중량 % 첨가하여， 균일하게 흔련 압출을 진행하고 펠렛을 제조하였다. Terephthalic acid-isosorbide 1, 4-cyclonucleic acid di-ethylene glycol copolymerized polyester resin (Tg: 120 ° C, number average molecular weight) using a biaxial kneading extruder (Φ: 40 mm, L / D = 40) 2.2 million) 60% by weight, terephthalic acid-isosorbide-1, 4-cyclonucleodiol diol- ethylene glycol copolymerized polyester resin (: 110 ° C, number average molecular weight: 2.5 million) 30% by weight, and methyl methacrylate- 0.5% by weight of acrylonitrile-styrene-glycidyl methacrylate, phenolic primary oxidant and phosphite secondary oxidant to 100% by weight of resin consisting of 10% by weight of butadiene-styrene graft copolymer 0.2 weight% was added and uniformly extrusion was performed and the pellet was manufactured.
상기에서， 테레프탈산-아이소소바이드 -1 , 4-사이클로핵산디올- 에틸렌글리콜 공중합 폴리에스테르 수지는 국내 에스케이케미칼사의 고충격 친환경수지인 에코젠 (EC0ZEN) , 메틸메타크릴레이트 -부타디엔-스티렌 그라프트 공중합체는 일본 KANEKA사의 코어-쉘 고무 (Core— Shel l Rubber )형태의 그라프트 MBS 제품인 M-300 , 아크릴로니트릴 -스티렌- 글리시딜 메타크릴레이트는 중국 SUNNY FC사의 SAG-005 , 페놀계 1차 산화안정제는 일본 ADEKA사의 A0-60 , 포스파이트계 2차 산화안정제는 미국 DOVER사의 S-9228 제품을 사용하였다. 실시예 5 In the above, terephthalic acid-isosorbide-1, 4-cyclonucleodiol diol-ethylene glycol copolymerized polyester resin is eco-enzyme (EC0ZEN), methyl methacrylate-butadiene-styrene graft air Incorporation of M-300, acrylonitrile-styrene-glycidyl methacrylate, a graft MBS product in the form of core-shell rubber of KANEKA, Japan, is SAG-005, phenolic 1 of SUNNY FC of China. The primary oxidative stabilizer was A0-60 from ADEKA, Japan, and the S-9228 from DOVER, USA, was used as a phosphite secondary oxidative stabilizer. Example 5
이축흔련압출기 (Φ : 40mm , L/D = 40)를 사용하여 사용하여 테레프탈산 -아이소소바이드 -1 , 4-사이클로핵산디올―에틸렌글리콜 공중합 폴리에스테르 수지 (Tg ： 120 °C , 수평균분자량 ： 2.2만) 50중량 %， 테레프탈산 -아이소소바이드 -1， 4-사이클로핵산디올-에틸렌글리콜 공증합 폴리에스테르 수지 (Tg ： 110°C , 수평균분자량 ： 2.5만) 40중량 %， 및
메틸메타크릴레이트 -부타디엔-스티렌 그라프트 공중합체 10중량 %로 이루어진 수지 100중량 %에 대해 아크릴로니트릴—스티렌-글리시딜 메타크릴레이트 0.5중량%, 페놀계 1차 산화안정제， 포스파이트계 2차 산화안정제를 각각 0.2중량 % 첨가하여， 균일하게 흔련 압출을 진행하고 펠렛을 제조하였다. Terephthalic Acid-Isosorbide-1, 4-cyclonucleic Acid Diol-Ethylene Glycol Copolymerized Polyester Resin (Tg: 120 ° C, Number-average Molecular Weight) Using a Biaxial Squeeze Extruder (Φ: 40mm, L / D = 40) 2.2 million) 50% by weight, terephthalic acid-iso carbide -1, 4-cyclonucleodiol diol-ethylene glycol co-condensed polyester resin (Tg: 110 ° C, number average molecular weight: 2.5 million) 40% by weight, and 0.5% by weight of acrylonitrile-styrene-glycidyl methacrylate to 100% by weight of resin consisting of 10% by weight of methyl methacrylate-butadiene-styrene graft copolymer, phenolic primary oxidative stabilizer, phosphite 2 0.2 wt% of the primary oxidative stabilizer was added to each other to uniformly carry out extrusion extrusion to prepare pellets.
상기에서， 테레프탈산-아이소소바이드 -1，4-사이클로핵산디올- 에틸렌글리콜 공중합 폴리에스테르 수지는 국내 에스케이케미칼사의 고충격 친환경수지인 에코젠 (EC0ZEN) , 메틸메타크릴레이트 -부타디엔-스티렌 그라프트 공중합체는 일본 RANEKA사의 코어-쉘 고무 (Core-She l l Rubber )형태의 그라프트 MBS 제품인 M-300 , 아크릴로니트랄ᅳ스티렌- 글리시딜 메타크릴레이트는 중국 SUNNY FC사의 SAG-005 , 페놀계 1차 산화안정제는 일본 ADEKA사의 A0-60 , 포스파이트계 2차 산화안정제는 미국 DOVER사의 S-9228 제품을 사용하였다. 비교예 1 내지 4 In the above, terephthalic acid-iso carbide-1, 4-cyclonucleodiol diol-ethylene glycol copolymerized polyester resin is Eco-Zen (EC0ZEN), methyl methacrylate-butadiene-styrene graft air Incorporation of M-300, acrylonitrile styrene-glycidyl methacrylate, a graft MBS product in the form of Core-Shell Rubber of RANEKA, Japan, is SAG-005, phenolic 1 of SUNNY FC of China. The primary oxidative stabilizer was A0-60 from ADEKA, Japan, and the S-9228 from DOVER, USA, was used as a phosphite secondary oxidative stabilizer. Comparative Examples 1 to 4
종래의 안경테용 플라스틱 제품을 하기와 같이 비교 대상으로 하였다. The conventional plastic product for eyeglass frames was compared as follows.
- 비교예 1 ： 폴리아미드 12 제품 Comparative Example 1 Polyamide 12 Product
- 비교예 2 ： 폴리에테르이미드 제품 Comparative Example 2: Polyetherimide Products
- 비교예 3 ： 폴리카보네이트 제품 Comparative Example 3 Polycarbonate Product
- 비교예 4 ： 폴리메틸메타크릴레이트 제품 Comparative Example 4: Polymethyl methacrylate product
<실험예: 고분자수지 조성물로부터 제조된 성형품의 물성 측정 > 상기 실시예 1 내지 5에 따라 제조된 펠렛， 및 상기 비교예 1 내지 4의 제품샘플을 사출기를 이용하여 사출온도 240 °C 에서 동일하게 사출한 후， 사출된 시험편을 23 ± 2 °C , 50 ± 5% 상대습도 조건 하에서 상태조절을 하고, 하기와 같이 기계적 물성을 측정하였다. 측정결과를 하기 표 1 및 2에 나타내었다. 실험예 1 ： 층격강도측정 <Experimental Example: Measurement of the physical properties of the molded article prepared from the polymer resin composition> The pellets prepared according to Examples 1 to 5, and the product samples of Comparative Examples 1 to 4 using the injection machine at the injection temperature 240 ° C. After injection, the injected test piece was controlled under 23 ± 2 ° C, 50 ± 5% relative humidity conditions, and the mechanical properties were measured as follows. The measurement results are shown in Tables 1 and 2 below. Experimental Example 1 ： Lamellar Strength Measurement
ASTM D 256 에 의거하여 측정용 시편을 만들어 아이조드
충격기 (Impact Tester, Toyoseiki)를 사용， 층격강도 값을 측정하였다. 실험예 2 ： 인장특성 측정 Izod made test specimen according to ASTM D 256 The stratification strength was measured using an impact tester (Impact Tester, Toyoseiki). Experimental Example 2 ： Tensile Characteristic Measurement
ASTM D 638 에 의거하여， 측정용 시편을 만들어 만능재료시험기 (Universal Testing Machine, Zwick Roe 11 Z010)를 사용하여 인장탄성율을 측정하였다. 실험예 3 ： 내열성 측정 In accordance with ASTM D 638, test specimens were made and tensile modulus was measured using a universal testing machine (Universal Testing Machine, Zwick Roe 11 Z010). Experimental Example 3 ： Heat Resistance Measurement
ASTM D 648 에 의거하여， 측정용 시편을 만들어 내열도시험기 (HDT Tester, Toyoseiki)를 사용하여 내열성을 측정하였다. 실험예 4 ： 투명도 측정 In accordance with ASTM D 648, the test specimen was made and the heat resistance was measured using a heat resistance tester (HDT Tester, Toyoseiki). Experimental Example 4 ： Transparency Measurement
ASTM D 1003 에 의거하여， 측정용 시편을 만들어 탁도계 (Hazemeter, Denshoku)를 사용하여 투명도를 측정하였다. In accordance with ASTM D 1003, test specimens were made and the transparency was measured using a turbidimeter (Hazemeter, Denshoku).
【표 1】 Table 1
【표 2】 Table 2
1 내지 4와 동등 수준 또는 그 이상으로 유지됨을 확인할 수 있다. 이에 따라， 상기 실시예 1 내지 5의 안경테는 환경친화적인 비이오수지를 포함하면서도， 종래의 안경테와 비슷한 수준의 물성을 구현해 낼 수 있는 우수한 친환경 소재임올 확인할 수 있다. It can be confirmed that it is maintained at the same level or more than 1 to 4. Accordingly, the spectacle frames of Examples 1 to 5 may be confirmed to be an excellent eco-friendly material that can realize the properties similar to those of the conventional spectacle frames, while including environmentally friendly non-resin.
또한， 실시예 1 내지 5의 안경테의 경우， 아이조드층격강도가 800 J/m 이상으로 측정되어， 아이조드충격강도가 700 J/m 미만인 비교예 1 내지 4의 안경테에 비해 월등히 향상된 충격강도를 나타냄을 확인할 수 있다. 이에 따라， 실시예 1 내지 5의 안경테의 경우， 두께가 얇아지더라도 쉽게 부러지지 않는 특성을 나타낼 수 있다.
In addition, in the case of the spectacle frames of Examples 1 to 5, the Izod layer strength was measured to be 800 J / m or more, showing that the Izod impact strength is significantly improved compared to the spectacle frame of Comparative Examples 1 to 4 with less than 700 J / m. You can check it. Accordingly, in the case of the spectacle frames of Examples 1 to 5, even if the thickness is thin may exhibit a characteristic that is not easily broken.
Claims
【청구항 1】 【Claim 1】
테레프탈산을 포함한 디카르복실산 성분의 잔기와, 디안히드로핵시를을 포함한 디올 성분의 잔기를 포함하는 폴리에스테르 수지 ; 및 A polyester resin containing a residue of a dicarboxylic acid component containing terephthalic acid and a residue of a diol component containing dianhydrohexyl; and
부타디엔계 공중합체를 포함한 코어， 아크릴레이트 /방향족 비닐 공중합체를 포함한 내층 쉘 및 방향족 비닐계 고분자를 포함한 외층 쉘을 포함하는 충격 보강재；를 포함하는， 안경테용 고분자 수지 조성물. A polymer resin composition for an eyeglass frame, comprising a core containing a butadiene-based copolymer, an impact reinforcing material containing an inner layer shell containing an acrylate/aromatic vinyl copolymer, and an outer layer shell containing an aromatic vinyl-based polymer.
【청구항 2】 【Claim 2】
제 1항에 있어서， In clause 1,
상기 층격 보강재의 함량이 전체 안경테용 고분자 수지 조성물 함량에 대하여 1 중량 % 내지 20 중량 %인， 안경테용 고분자 수지 조성물. A polymer resin composition for an eyeglasses frame, wherein the content of the impact reinforcement material is 1% by weight to 20% by weight based on the total content of the polymer resin composition for an eyeglasses frame.
【청구항 3】 【Claim 3】
게 1항에 있어서， In paragraph 1,
상기 코어는 부타디엔 단량체 30 중량 % 내지 100 중량 %， 방향족 비닐 단량체 0 중량 % 내지 70 중량 ¾>， 공중합가능한 비닐계 단량체 0 중량 % 내지 10 중량 %， 가교성 단량체 0 중량 % 내지 5 증량 %를 함유하는 단량체 흔합물올 중합하여 얻어지는 부타디엔계 공증합체를 포함하고， The core contains 30% to 100% by weight of butadiene monomer, 0% to 70% by weight of aromatic vinyl monomer, 0% to 10% by weight of copolymerizable vinyl monomer, and 0% to 5% by weight of crosslinkable monomer. It includes a butadiene-based copolymer obtained by polymerizing a monomer mixture,
상기 내층 쉘은 방향족 비닐 단량체 60 증량 % 내지 98 중량 %， 히드록실기를 함유하는 (메타)아크릴산에스테르 단량체 2 중량 % 내지 40 중량 %， 공중합가능한 비닐계 단량체 0 증량 % 내지 20 중량 %를 함유하는 단량체. 흔합물을 중합하여 얻어지는 아크릴레이트 /방향족 비닐 공중합체를 포함하며， The inner layer shell contains 60% to 98% by weight of an aromatic vinyl monomer, 2% to 40% by weight of a (meth)acrylic acid ester monomer containing a hydroxyl group, and 0% to 20% by weight of a copolymerizable vinyl monomer. Monomer. Contains an acrylate/aromatic vinyl copolymer obtained by polymerizing a mixture,
상기 외층 쉘은 방향족 비닐 단량체 10 중량 % 내지 100 중량 %， 알킬 (메타)아크릴레이트 0 중량 % 내지 90 중량 %， 공중합가능한 비닐계 단량체 0 중량 ¾> 내지 50 중량 %를 함유하는 단량체 흔합물을 중합하여 얻어지는 방향족 비닐계 고분자를 포함하는， 안경테용 고분자 수지 조성물.
The outer layer shell is polymerized with a monomer mixture containing 10% to 100% by weight of aromatic vinyl monomer, 0% to 90% by weight of alkyl (meth)acrylate, and 0% to 50% by weight of copolymerizable vinyl monomer. A polymer resin composition for an eyeglass frame containing an aromatic vinyl polymer obtained by:
【청구항 4】 【Claim 4】
게 1항에 있어서， In paragraph 1,
상기 폴리에스테르 수지는, 유리전이온도가 115°C 내지 125°C이고 수평균분자량이 16,000 내지 26,000인 폴리에스테르 수지 및 유리전이온도가 105 °C 내지 115°C이고 수평균분자량이 20,000 내지 30,000인 폴리에스테르 수지로 이루어진 군으로부터 선택되는 1종 이상을 포함하는， 안경테용 고분자 수지 조성물. The polyester resin has a glass transition temperature of 115 ° C to 125 ° C and a number average molecular weight of 16,000 to 26,000, and a glass transition temperature of 105 ° C to 115 ° C and a number average molecular weight of 20,000 to 30,000. A polymer resin composition for an eyeglass frame, comprising at least one member selected from the group consisting of polyester resin.
【청구항 5】 【Claim 5】
제 4항에 있어서， In clause 4,
상기 유리전이온도가 115°C 내지 125°C이고 수평균분자량이 16,000 내지 26,000인 폴리에스테르 수지 및 유리전이온도가 105°C 내지 115°C이고 수평균분자량이 20,000 내지 30,000인 폴리에스테르 수지의 중량비가 0.5:1 내지 5:1인， 안경테용 고분자 수지 조성물. 一 Weight ratio of the polyester resin having a glass transition temperature of 115 ° C to 125 ° C and a number average molecular weight of 16,000 to 26,000 and a polyester resin having a glass transition temperature of 105 ° C to 115 ° C and a number average molecular weight of 20,000 to 30,000 A polymer resin composition for eyeglass frames, where the ratio is 0.5:1 to 5:1. 1
【청구항 6】 【Claim 6】
게 1항에 있어서， In paragraph 1,
상기 폴리에스테르 수지에 포함된 디카르복실산 성분은 탄소수 8 내지 20의 방향족 디카르복실산 및 탄소수 4 내지 20의 지방족 디카르복실산으로 이루어진 군으로부터 선택되는 1종 이상을 더 포함하는， 안경테용 고분자 수지 조성물. The dicarboxylic acid component contained in the polyester resin further includes at least one selected from the group consisting of aromatic dicarboxylic acids having 8 to 20 carbon atoms and aliphatic dicarboxylic acids having 4 to 20 carbon atoms. Polymer resin composition.
【청구항 7】 【Claim 7】
제 1항에 있어서， In clause 1,
상기 폴리에스테르 수지에 포함된 디안히드로핵시를은 아이소소바이드인， 안경테용 고분자 수지 조성물.. The dianhydrohexyl contained in the polyester resin is isosorbide, a polymer resin composition for eyeglass frames.
【청구항 8】 【Claim 8】
제 1항에 있어서， In clause 1,
상기 폴리에스테르 수지에 포함된 디안히드로핵시를의 함량은 전체
디을 성분의 함량에 대하여 5 몰% 내지 60 몰%인， 안경테용 고분자 수지 조성물. The content of dianhydrohexyl contained in the polyester resin is A polymer resin composition for eyeglass frames, which is 5 mol% to 60 mol% based on the content of the diol component.
【청구항 9】 【Claim 9】
제 1항에 있어서， In clause 1,
상기 폴리에스테르 수지에 포함된 디올 성분은 하기 화학식 1， 2 및 3으로 표시되는 화합물들로 이루어진 군으로부터 선택되는 1종 이상을 더 포함하는, 안경테용 고분자 수지 조성물: The diol component contained in the polyester resin further includes at least one selected from the group consisting of compounds represented by the following formulas 1, 2, and 3:
[화학식 1] [Formula 1]
상기 화학식 1에서, , ¾ 및 는 각각 독립적으로 수소 또는 탄소수 1 내지 5 의 치환 또는 비치환된 알킬기이며， 및 n2 는 각각 독립적으로 0 내지 3의 정수이고， In Formula 1, , ¾ and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and n 2 are each independently an integer of 0 to 3,
[화학식 2] [Formula 2]
상기 화학식 2에서， R5 , R6 , R7 및 R8는 각각 독립적으로 수소 또는 탄소수 1 내지 5 의 치환 또는 비치환된 알킬기이며 , In Formula 2, R 5 , R 6 , R 7 and R 8 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,
[화학식 3]
상기 화학식 3에서， n읔 1 내지 7의 정수이다. [Formula 3] In Formula 3, n is an integer from 1 to 7.
【청구항 10】 【Claim 10】
제 1항에 있어서， In clause 1,
상기 폴리에스테르 수지에 포함된 디올 성분은 1，4-사이클로핵산디올 및 에틸렌글리콜을 더 포함하는， 안경테용 고분자 수지 조성물. A polymer resin composition for an eyeglass frame, wherein the diol component contained in the polyester resin further includes 1,4-cyclohexane diol and ethylene glycol.
【청구항 11】 【Claim 11】
제 1항의 고분자 수지 조성물의 성형품을 포함하는， 안경테.
An eyeglasses frame comprising a molded article of the polymer resin composition of claim 1.
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| KR102357084B1 (en) * | 2015-08-26 | 2022-01-27 | 에스케이케미칼 주식회사 | Polymer resin composition and molded product of the same |
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