JP2018138641A - Chlorine-containing resin composition and molding using the same - Google Patents
Chlorine-containing resin composition and molding using the same Download PDFInfo
- Publication number
- JP2018138641A JP2018138641A JP2017033655A JP2017033655A JP2018138641A JP 2018138641 A JP2018138641 A JP 2018138641A JP 2017033655 A JP2017033655 A JP 2017033655A JP 2017033655 A JP2017033655 A JP 2017033655A JP 2018138641 A JP2018138641 A JP 2018138641A
- Authority
- JP
- Japan
- Prior art keywords
- chlorine
- resin composition
- containing resin
- acid
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000460 chlorine Substances 0.000 title claims abstract description 49
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 49
- 238000000465 moulding Methods 0.000 title abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000011701 zinc Substances 0.000 claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 159000000009 barium salts Chemical class 0.000 claims abstract description 17
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 claims abstract description 17
- 239000000845 maltitol Substances 0.000 claims abstract description 17
- 235000010449 maltitol Nutrition 0.000 claims abstract description 17
- 229940035436 maltitol Drugs 0.000 claims abstract description 17
- 150000007524 organic acids Chemical class 0.000 claims abstract description 17
- 239000004014 plasticizer Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 abstract description 15
- -1 zinc-modified hydrotalcite compound Chemical class 0.000 description 45
- 229920001577 copolymer Polymers 0.000 description 16
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 description 6
- 229960001545 hydrotalcite Drugs 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- RYOLIMKPFQALMC-UHFFFAOYSA-L zinc;4-methylbenzoate Chemical compound [Zn+2].CC1=CC=C(C([O-])=O)C=C1.CC1=CC=C(C([O-])=O)C=C1 RYOLIMKPFQALMC-UHFFFAOYSA-L 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- NRLOQEQAWOKEJF-UHFFFAOYSA-N (6-methyl-1,1-diphenylheptyl) dihydrogen phosphite Chemical compound C=1C=CC=CC=1C(OP(O)O)(CCCCC(C)C)C1=CC=CC=C1 NRLOQEQAWOKEJF-UHFFFAOYSA-N 0.000 description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 2
- FGYJSJUSODGXAR-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-octoxy-5h-benzo[d][1,3,2]benzodioxaphosphocine Chemical compound C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP(OCCCCCCCC)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C FGYJSJUSODGXAR-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- OZOAMTISPPUGSQ-UHFFFAOYSA-N 4-[14,16-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-15,15,16,17-tetra(tridecyl)triacontan-14-yl]-2-tert-butyl-5-methylphenol phosphorous acid Chemical compound OP(O)O.OP(O)O.OP(O)O.C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCCCCCCCCCCCC)(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C(CCCCCCCCCCCCC)(CCCCCCCCCCCCC)C(CCCCCCCCCCCCC)(C(CCCCCCCCCCCCC)CCCCCCCCCCCCC)C1=CC(C(C)(C)C)=C(O)C=C1C OZOAMTISPPUGSQ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZCGNNESZWJPBLW-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite 2-[2-(2-hydroxyphenyl)propan-2-yl]-3,4,5,6-tetra(tridecyl)phenol Chemical compound OP(O)OP(O)O.CCCCCCCCCCCCCC1=C(CCCCCCCCCCCCC)C(CCCCCCCCCCCCC)=C(O)C(C(C)(C)C=2C(=CC=CC=2)O)=C1CCCCCCCCCCCCC ZCGNNESZWJPBLW-UHFFFAOYSA-N 0.000 description 2
- OGVJEUDMQQIAPV-UHFFFAOYSA-N diphenyl tridecyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCCCCC)OC1=CC=CC=C1 OGVJEUDMQQIAPV-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 235000013872 montan acid ester Nutrition 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- 229940098697 zinc laurate Drugs 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- QQGRFMIMXPWKPM-UHFFFAOYSA-N 2,3,4-tributylphenol Chemical compound CCCCC1=CC=C(O)C(CCCC)=C1CCCC QQGRFMIMXPWKPM-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- ZSMMOCNTIRCAAL-UHFFFAOYSA-N 2-[2-[2-[2-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 2-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound C=1C(C)=C(O)C(C(C)(C)C)=CC=1C(C)C(=O)OCCOCCOCCOC(=O)C(C)C1=CC(C)=C(O)C(C(C)(C)C)=C1 ZSMMOCNTIRCAAL-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 2-dodecanoyloxyethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCC ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920005671 poly(vinyl chloride-propylene) Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 1
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- WRSPWQHUHVRNFV-UHFFFAOYSA-N tris[3,5-di(nonyl)phenyl] phosphite Chemical compound CCCCCCCCCC1=CC(CCCCCCCCC)=CC(OP(OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)=C1 WRSPWQHUHVRNFV-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- JBCJMTUHAXHILC-UHFFFAOYSA-N zinc;octanoic acid Chemical compound [Zn+2].CCCCCCCC(O)=O JBCJMTUHAXHILC-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
Abstract
Description
本発明は、塩素含有樹脂組成物及びそれを用いた成形体に関する。 The present invention relates to a chlorine-containing resin composition and a molded body using the same.
ポリ塩化ビニルに代表される塩素含有樹脂は、柔軟性が高く加工しやすいうえ、機械的強度等の物性も有するため、管路材料の他、種々様々な用途に広く使用されている。だが一方で、塩素含有樹脂は熱安定性に課題があり、加工時や使用時の熱に不安定で加熱により分解が生じることから、熱安定性や加工性向上の観点から、塩素含有樹脂とともに安定剤が併用されるのが通常である。 Chlorine-containing resins typified by polyvinyl chloride are flexible and easy to process, and have physical properties such as mechanical strength. Therefore, they are widely used in various applications in addition to pipe materials. However, chlorine-containing resins have problems with thermal stability, and are unstable to heat during processing and use and decompose due to heating, so from the viewpoint of improving thermal stability and workability, together with chlorine-containing resins A stabilizer is usually used in combination.
安定剤としては従来、錫、鉛、カドミウム等の重金属系安定剤が一般に使用されてきたが、近年の環境問題への意識の高まりからこれらの重金属の使用が忌避されつつある。そこで、例えば、バリウム亜鉛系（Ｂａ／Ｚｎ）やカルシウム亜鉛系（Ｃａ／Ｚｎ）と称される安定剤の他、糖アルコール類とハイドロタルサイトとの併用系（特許文献１参照）、有機酸亜鉛塩と亜鉛変性ハイドロタルサイト系化合物と糖アルコール類との併用系（特許文献２参照）等の安定剤も開発されている。 Conventionally, heavy metal stabilizers such as tin, lead, cadmium and the like have been generally used as stabilizers, but the use of these heavy metals is being repelled due to the recent increase in awareness of environmental problems. Therefore, for example, in addition to stabilizers called barium zinc (Ba / Zn) and calcium zinc (Ca / Zn), a combination system of sugar alcohols and hydrotalcite (see Patent Document 1), organic acid Stabilizers such as a combined system of a zinc salt, a zinc-modified hydrotalcite compound and a sugar alcohol (see Patent Document 2) have also been developed.
上述のとおり種々の安定剤が開発されている。だが、バリウム亜鉛系やカルシウム亜鉛系の安定剤を塩素含有樹脂に使用しても耐熱性が充分とはならないため、厳しい成型条件で加工を行うことができない。また過塩基性のバリウム塩は、耐熱性安定剤として知られているものの、透明性及び色調の点で課題がある。このように従来の安定剤を塩素含有樹脂に使用した場合、樹脂組成物の耐熱性を向上することができても透明性及び色調を大幅に損ないやすく、逆に透明性や色調を向上させると耐熱性が大幅に低下するため、成形品において高透明性と高耐熱性とを両立することができなかった。なお、特許文献１、２に記載の安定剤は、粉体状態でポリ塩化ビニルに混練しているが、耐熱性が充分ではないうえ、透明性や色調の点でも課題がある。また、工業板用途といった硬質透明樹脂組成物においては、特に高い透明性と耐熱性が要求されるが、これらの安定剤は、透明性及び耐熱性のいずれも不充分であった。更に、工業板用途の中でも波板等の用途では、耐酸性も兼ね備える必要があるが、これらの安定剤では耐酸性も不充分であった。 As described above, various stabilizers have been developed. However, even if barium zinc-based or calcium zinc-based stabilizers are used in the chlorine-containing resin, the heat resistance is not sufficient, so that processing cannot be performed under severe molding conditions. Further, overbased barium salts are known as heat-resistant stabilizers, but have problems in terms of transparency and color tone. As described above, when the conventional stabilizer is used for the chlorine-containing resin, even if the heat resistance of the resin composition can be improved, the transparency and color tone are likely to be greatly impaired, and conversely, the transparency and color tone are improved. Since the heat resistance is greatly lowered, it was impossible to achieve both high transparency and high heat resistance in the molded product. The stabilizers described in Patent Documents 1 and 2 are kneaded with polyvinyl chloride in a powder state, but the heat resistance is not sufficient, and there are also problems in terms of transparency and color tone. Moreover, in the hard transparent resin composition for industrial board use, particularly high transparency and heat resistance are required, but these stabilizers are insufficient in both transparency and heat resistance. Furthermore, among industrial plate applications, it is necessary to have acid resistance in applications such as corrugated sheets, but these stabilizers have insufficient acid resistance.
本発明は、上記現状に鑑み、高透明性と高耐熱性とを両立することができ、かつ耐酸性にも優れる成形品を与えることができる塩素含有樹脂組成物を提供することを目的とする。また、このような塩素含有樹脂組成物を用いてなる成形体を提供することも目的とする。 In view of the above situation, the present invention aims to provide a chlorine-containing resin composition that can achieve both high transparency and high heat resistance, and can provide a molded product having excellent acid resistance. . Another object of the present invention is to provide a molded article using such a chlorine-containing resin composition.
本発明者らは、塩素含有樹脂組成物について鋭意検討を進めるうち、塩素含有樹脂とともに、過塩基性バリウム塩及び有機酸亜鉛を含む液状安定剤とマルチトールとをそれぞれ所定量含む樹脂組成物とすると、特異的に高透明性と高耐熱性とを兼ね備えた成形体が得られることを見いだした。これは、過塩基性バリウム塩及び有機酸亜鉛を含む液状安定剤は粉状の安定剤に比べて分散性が高く、かつ耐熱性が高いうえ、マルチトールが塩素含有樹脂になじみやすいことに起因するものと考えられる。このような樹脂組成物は、可塑剤を含まない又は含んでも微量である場合にも、透明性及び耐熱性のいずれにも優れる成形品を与えることができるため、硬質樹脂用途に特に有用であり、塩素含有樹脂の成形体分野に多大な貢献をなすものである。また、このような樹脂組成物を用いて得られる成形体は、耐酸性にも優れるうえ、その成型時に、プレートアウト（すなわち金型やサイジング等に樹脂組成物が付着する現象）の発生や発泡を充分に抑制することもできる。それゆえ、プレートアウト発生に伴う金型やサイジング等の洗浄作業を省略又は簡略化することができ、成形体の生産性の点でも有利である。こうして上記課題をみごとに解決することができることに想到し、本発明を完成するに至った。 As the inventors proceeded diligently to study the chlorine-containing resin composition, together with the chlorine-containing resin, a liquid composition containing an overbased barium salt and an organic acid zinc and maltitol, respectively, and a resin composition containing a predetermined amount, As a result, it has been found that a molded body having both high transparency and high heat resistance can be obtained. This is because liquid stabilizers containing overbased barium salts and organic acid zinc have higher dispersibility and higher heat resistance than powdered stabilizers, and maltitol is easily compatible with chlorine-containing resins. It is thought to do. Such a resin composition is particularly useful for hard resin applications because it can provide a molded article that is excellent in both transparency and heat resistance even when it contains no plasticizer or is contained in a trace amount. It makes a great contribution to the field of molded products of chlorine-containing resins. In addition, a molded product obtained using such a resin composition is excellent in acid resistance, and at the time of molding, plate-out (that is, a phenomenon in which the resin composition adheres to a mold, sizing, etc.) or foaming occurs. Can be sufficiently suppressed. Therefore, it is possible to omit or simplify the cleaning work such as die and sizing accompanying the occurrence of plate-out, which is advantageous in terms of the productivity of the molded body. Thus, the inventors have conceived that the above problems can be solved brilliantly, and have completed the present invention.
すなわち本発明は、塩素含有樹脂１００重量部に対し、過塩基性バリウム塩及び有機酸亜鉛を含む液状安定剤１〜１０重量部と、マルチトール０．０１〜１重量部とを含む塩素含有樹脂組成物である。
上記塩素含有樹脂組成物中の可塑剤の含有量は、塩素含有樹脂組成物１００質量％に対して０〜５質量％であることが好ましい。
That is, the present invention relates to a chlorine-containing resin comprising 1 to 10 parts by weight of a liquid stabilizer containing an overbased barium salt and an organic acid zinc and 0.01 to 1 part by weight of maltitol with respect to 100 parts by weight of the chlorine-containing resin. It is a composition.
It is preferable that content of the plasticizer in the said chlorine containing resin composition is 0-5 mass% with respect to 100 mass% of chlorine containing resin compositions.
本発明はまた、上記塩素含有樹脂組成物を用いてなる成形体でもある。
上記成形体は、透明成形体であることが好ましい。
上記成形体はまた、板状、フィルム状又はシート状であることが好ましい。
The present invention is also a molded article using the chlorine-containing resin composition.
The molded body is preferably a transparent molded body.
The molded body is preferably plate-shaped, film-shaped or sheet-shaped.
本発明の塩素含有樹脂組成物は、高透明性と高耐熱性とを両立することができ、かつ耐酸性にも優れる成形品を与えることができる。この成形品は、塩素含有樹脂由来の各種物性に優れるうえ、初期着色が小さいため、鮮やかな色調を奏することもできる。また、この樹脂組成物は、錫、鉛、カドミウム等の重金属成分を含有しないものとすることもできるため、近年の安全性を求めるニーズにも充分に対応することができ、極めて有用である。更に、この樹脂組成物を用いれば、成型時に、プレートアウトの発生や発泡を充分に抑制することもできるため、成形体の生産性の点でも有利である。 The chlorine-containing resin composition of the present invention can provide a molded product that can achieve both high transparency and high heat resistance and is excellent in acid resistance. This molded article is excellent in various physical properties derived from the chlorine-containing resin, and can also produce a vivid color tone because the initial coloring is small. Moreover, since this resin composition can also be a thing which does not contain heavy metal components, such as tin, lead, and cadmium, it can fully respond to the need for the recent safety | security and is very useful. Furthermore, if this resin composition is used, the occurrence of plate-out and foaming can be sufficiently suppressed during molding, which is advantageous in terms of the productivity of the molded product.
以下、本発明の好ましい形態について具体的に説明するが、本発明は以下の記載のみに限定されるものではなく、本発明の要旨を変更しない範囲において適宜変更して適用することができる。 Hereinafter, although the preferable form of this invention is demonstrated concretely, this invention is not limited only to the following description, In the range which does not change the summary of this invention, it can change suitably and can apply.
本明細書中、「液状」とは、０〜３５℃の任意の温度で液状であることを意味する。
「液状安定剤」とは、２５℃における粘度が１００００ｃｐｓ以下であり、かつ０〜３５℃の任意の温度で液状であり、含有成分が溶媒に溶解しているものである。
In this specification, “liquid” means liquid at an arbitrary temperature of 0 to 35 ° C.
The “liquid stabilizer” is a liquid having a viscosity at 25 ° C. of 10,000 cps or less and in a liquid state at an arbitrary temperature of 0 to 35 ° C., and the contained components are dissolved in a solvent.
１、塩素含有樹脂組成物
本発明の塩素含有樹脂組成物（単に「樹脂組成物」とも称す）は、塩素含有樹脂と、過塩基性バリウム塩及び有機酸亜鉛を含む液状安定剤と、マルチトールとを含む。必要に応じ更に他の成分を含んでもよく、各含有成分はそれぞれ１種又は２種以上であってもよい。
1. Chlorine-containing resin composition The chlorine-containing resin composition of the present invention (also simply referred to as “resin composition”) comprises a chlorine-containing resin, a liquid stabilizer containing an overbased barium salt and an organic acid zinc, and maltitol. Including. If necessary, it may further contain other components, and each of the components may be one type or two or more types.
１）塩素含有樹脂
塩素含有樹脂は、塩素原子を含む樹脂（重合体）である限り特に限定されないが、塩化ビニル系樹脂が好ましい。これにより、柔軟性や難燃性に優れる成形体が得られる。
1) Chlorine-containing resin The chlorine-containing resin is not particularly limited as long as it is a resin (polymer) containing chlorine atoms, but a vinyl chloride resin is preferable. Thereby, the molded object which is excellent in a softness | flexibility and a flame retardance is obtained.
塩化ビニル系樹脂としては、例えば、ポリ塩化ビニル、塩素化ポリ塩化ビニル、ポリ塩化ビニリデン、塩素化ポリエチレン等の単独重合体；塩化ビニル−酢酸ビニル共重合体、塩化ビニル−エチレン−酢酸ビニル共重合体、塩化ビニル−エチレン共重合体、塩化ビニル−プロピレン共重合体、塩化ビニル−スチレン共重合体、塩化ビニル−イソブチレン共重合体、塩化ビニル−塩化ビニリデン共重合体、塩化ビニル−ウレタン共重合体、塩化ビニル−アクリル酸エステル共重合体、塩化ビニル−スチレン−無水マレイン酸共重合体、塩化ビニル−スチレン−アクリロニトリル共重合体、塩化ビニル−ブタジエン共重合体、塩化ビニル−イソプレン共重合体、塩化ビニル−塩素化プロピレン共重合体、塩化ビニル−塩化ビニリデン−酢酸ビニル共重合体、塩化ビニル−マレイン酸エステル共重合体、塩化ビニル−メタクリル酸エステル共重合体、塩化ビニル−アクリロニトリル共重合体、塩化ビニル−マレイミド共重合体等の共重合体；等が挙げられる。
なお、塩素含有樹脂と塩素非含有樹脂とのブレンド品を使用してもよいし、また塩化ビニル系樹脂を得るための重合方法は特に限定されない。
Examples of the vinyl chloride resin include homopolymers such as polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, and chlorinated polyethylene; vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate copolymer Polymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer , Vinyl chloride-acrylic acid ester copolymer, vinyl chloride-styrene-maleic anhydride copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, chloride Vinyl-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate Polymers, vinyl chloride - maleic acid ester copolymer, vinyl chloride - methacrylic acid ester copolymers, vinyl chloride - acrylonitrile copolymer, vinyl chloride - copolymers such as maleimide copolymer; and the like.
A blend of a chlorine-containing resin and a chlorine-free resin may be used, and the polymerization method for obtaining a vinyl chloride resin is not particularly limited.
塩化ビニル系樹脂はまた、ペースト塩化ビニル樹脂よりも、ストレート塩化ビニル樹脂であることが好適である。これにより、透明用途により好適なものとなる。 The vinyl chloride resin is also preferably a straight vinyl chloride resin rather than a paste vinyl chloride resin. Thereby, it becomes a more suitable thing for a transparent use.
２）液状安定剤
本発明では、過塩基性バリウム塩及び有機酸亜鉛を含む液状安定剤を用いる。
このような液状安定剤は、粉状安定剤に比べて分散性が高く、液状安定剤自体の透明性も高いため、高い透明性を維持した成形体を与えることができる。また、成形体の耐酸性を高め、プレートアウト抑制能、発泡抑制能を発揮することもできる。なお、過塩基性バリウム塩及び有機酸亜鉛はそれぞれ１種又は２種以上を使用することができる。
2) Liquid stabilizer In the present invention, a liquid stabilizer containing an overbased barium salt and an organic acid zinc is used.
Such a liquid stabilizer has a higher dispersibility than the powdery stabilizer, and the liquid stabilizer itself has high transparency, so that a molded product maintaining high transparency can be provided. Moreover, the acid resistance of a molded object can be improved and plate out suppression ability and foam suppression ability can also be exhibited. In addition, an overbased barium salt and organic acid zinc can use 1 type (s) or 2 or more types, respectively.
−有機酸亜鉛−
有機酸亜鉛としては、亜鉛とカルボン酸とからなる塩であることが好ましい。カルボン酸としては特に限定されず、脂肪族カルボン酸であってもよいし、芳香族カルボン酸であってもよい。脂肪族カルボン酸が有する脂肪族骨格を構成する炭素数も特に限定されないが、例えば１〜２０であることが好ましく、より好ましくは５〜１０である。カルボン酸が有するカルボキシル基の数も特に限定されず、モノカルボン酸、ジカルボン酸、トリカルボン酸等のいずれであってもよい。中でも、耐熱性の観点でモノカルボン酸が好ましく、より好ましくは炭素数５〜１０の脂肪族カルボン酸又は芳香族カルボン酸である。有機酸亜鉛として特に好ましくは、本発明の作用効果をより発揮できるようにする観点から、オクチル酸亜鉛やトルイル酸亜鉛であり、最も好ましくはトルイル酸亜鉛である。
なお、トルイル酸亜鉛としては、ｏ−、ｐ−、ｍ−のいずれも好ましく使用することができるが、透明性を更に高める観点から、ｍ−トルイル酸亜鉛（メタトルイル酸亜鉛とも称す）が好適である。
-Organic acid zinc-
The organic acid zinc is preferably a salt composed of zinc and a carboxylic acid. It does not specifically limit as carboxylic acid, Aliphatic carboxylic acid may be sufficient and aromatic carboxylic acid may be sufficient. Although carbon number which comprises the aliphatic skeleton which aliphatic carboxylic acid has is also not specifically limited, For example, it is preferable that it is 1-20, More preferably, it is 5-10. The number of carboxyl groups possessed by the carboxylic acid is not particularly limited, and may be any of monocarboxylic acid, dicarboxylic acid, tricarboxylic acid and the like. Among these, monocarboxylic acids are preferable from the viewpoint of heat resistance, and more preferable are aliphatic carboxylic acids or aromatic carboxylic acids having 5 to 10 carbon atoms. Particularly preferred as the organic acid zinc is zinc octylate or zinc toluate, most preferably zinc toluate, from the viewpoint of enabling the operational effects of the present invention to be exhibited more.
In addition, as zinc toluate, any of o-, p-, and m- can be preferably used, but m-toluic acid zinc (also referred to as zinc metatoluic acid) is preferable from the viewpoint of further improving transparency. is there.
液状安定剤中の有機酸亜鉛は、液状安定剤の総量１００質量％に対し、１〜３０質量％であることが好ましく、２〜２０質量％であることがより好ましく、５〜１５質量％であることが更に好ましい。 The organic acid zinc in the liquid stabilizer is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and 5 to 15% by mass with respect to 100% by mass of the total amount of the liquid stabilizer. More preferably it is.
−過塩基性バリウム塩−
過塩基性バリウム塩としては特に限定されないが、例えば、過塩基性オレイン酸バリウム塩、過塩基性ネオデカン酸バリウム塩等が挙げられる。具体的には、例えば、ＡＭスタビライザーズ社製のプラスチスタブ２１０６、プラスチスタブ２１１６、プラスチスタブ２５０８、プラスチスタブ２５１３等が好適である。
-Overbased barium salt-
Although it does not specifically limit as an overbased barium salt, For example, an overbased barium oleate salt, an overbased barium neodecanoate salt, etc. are mentioned. Specifically, for example, a plastic stub 2106, a plastic stub 2116, a plastic stub 2508, and a plastic stub 2513 manufactured by AM Stabilizers are suitable.
液状安定剤中の過塩基性バリウム塩は、液状安定剤の総量１００質量％に対し、５〜８０質量％であることが好ましく、３０〜７０質量％であることがより好ましく、４５〜６５質量％であることが更に好ましい。 The overbased barium salt in the liquid stabilizer is preferably 5 to 80% by mass, more preferably 30 to 70% by mass, and more preferably 45 to 65% by mass with respect to 100% by mass of the total amount of the liquid stabilizer. % Is more preferable.
液状安定剤中の有機酸亜鉛と過塩基性バリウム塩との合計含有量は、液状安定剤の総量１００質量％に対し、３５質量％以上であることが好ましく、４０質量％以上であることがより好ましく、５０質量％以上であることが更に好ましい。 The total content of the organic acid zinc and the overbased barium salt in the liquid stabilizer is preferably 35% by mass or more and 40% by mass or more with respect to 100% by mass of the total amount of the liquid stabilizer. More preferably, it is more preferably 50% by mass or more.
−リン化合物−
液状安定剤は、リン化合物を更に含むことが好適である。中でも、ホスファイト化合物が好ましく、これにより、成形品において透明性や色調、耐候性等の種々の物性がより向上される。
-Phosphorus compounds-
It is preferable that the liquid stabilizer further contains a phosphorus compound. Among these, phosphite compounds are preferable, and various physical properties such as transparency, color tone, and weather resistance are further improved in the molded product.
ホスファイト化合物としては特に限定されないが、例えば、トリフェニルホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、トリス（ノニルフェニル）ホスファイト、トリス（ジノニルフェニル）ホスファイト、トリス（モノ、ジ混合ノニルフェニル）ホスファイト、ジフェニルアシッドホスファイト、２，２'−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト、ジフェニルデシルホスファイト、ジフェニルイソオクチルフォスファイト、ジフェニルトリデシルフォスファイト、フェニルジイソデシルホスファイト、トリブチルホスファイト、トリ（２−エチルヘキシル）ホスファイト、トリデシルホスファイト、トリラウリルホスファイト、ジブチルアシッドホスファイト、ジラウリルアシッドホスファイト、トリラウリルトリチオホスファイト、ビス（ネオペンチルグリコール）・１，４−シクロヘキサンジメチルジホスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、フェニル−４，４' −イソプロピリデンジフェノール・ペンタエリスリトールジホスファイト、テトラ（Ｃ１２〜１５混合アルキル）−４，４' −イソプロピリデンジフェニルジホスファイト、水素化−４，４' −イソプロピリデンジフェノールポリホスファイト、ビス（オクチルフェニル）・ビス〔４，４' −ｎ−ブチリデンビス（２−ｔ−ブチル−５−メチルフェノール）〕・１，６−ヘキサンジオール・ジホスファイト、テトラトリデシル・４，４' −ブチリデンビス（２−ｔ−ブチル−５−メチルフェノール）ジホスファイト、ヘキサ（トリデシル）・１，１，３−トリス（２−メチル−５−ｔ−ブチル−４−ヒドロキシフェニル）ブタン・トリホスファイト、９，１０−ジハイドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド等が挙げられる。 Although it does not specifically limit as a phosphite compound, For example, a triphenyl phosphite, a tris (2, 4- di-t- butylphenyl) phosphite, a tris (nonylphenyl) phosphite, a tris (dinonylphenyl) phosphite, Tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, diphenyldecyl phosphite, diphenylisooctyl phosphite, Diphenyl tridecyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acyl Phosphite, trilauryl trithiophosphite, bis (neopentylglycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6- Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl-4,4′-isopropylidenediphenol pentaerythritol diphosphite, tetra (C 12-15 mixed) Alkyl) -4,4'-isopropylidene diphenyl diphosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) .bis [4,4'-n-butylidenebis (2- t-Butyl-5-methylphenol 1,6-hexanediol diphosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane triphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like.
上記の他、トリスノニルフェニルホスファイト、トリス（２，４−ジ第三ブチルフェニル）ホスファイト、トリス〔２−第三ブチル−４−（３−第三ブチル−４−ヒドロキシ−５−メチルフェニルチオ）−５−メチルフェニル〕ホスファイト、トリデシルホスファイト、オクチルジフェニルホスファイト、ジ（デシル）モノフェニルホスファイト、モノデシルジフェニルホスファイト、モノ（ジノニルフェニル）ビス（ノニルフェニル）ホスファイト、ジ（トリデシル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４−ジ第三ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ第三ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（Ｃ１２〜１５混合アルキル）−４，４’−ｎ−ブチリデンビス（２−第三ブチル−５−メチルフェノール）ジホスファイト、ヘキサ（トリデシル）−１，１，３−トリス（２−メチル−４−ヒドロキシ−５−第三ブチルフェニル）ブタントリホスファイト、テトラキス（２，４−ジ第三ブチルフェニル）ビフェニレンジホスホナイト、２，２’−メチレンビス（４，６−ジ第三ブチルフェニル）（オクチル）ホスファイト等も挙げられる。 In addition to the above, trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenyl) Thio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, monodecyl diphenyl phosphite, mono (dinonylphenyl) bis (nonylphenyl) phosphite, Di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphosphite, bis (2 , 6-Ditert-butyl-4- Butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (C 12 to 15 mixed alkyl)-4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2, Examples include 4-ditertiarybutylphenyl) biphenylene diphosphonite, 2,2′-methylenebis (4,6-ditertiarybutylphenyl) (octyl) phosphite, and the like.
液状安定剤がリン化合物（好ましくはホスファイト化合物）を含む場合、その含有量は特に限定されないが、例えば、液状安定剤の総量１００質量％に対し、０〜３０質量％が好ましい。これにより、リン化合物由来の効果をより発揮することが可能になる。より好ましくは５〜２５質量％、更に好ましくは１５〜２５質量％である。 When the liquid stabilizer contains a phosphorus compound (preferably a phosphite compound), the content is not particularly limited. For example, 0 to 30% by mass is preferable with respect to 100% by mass of the liquid stabilizer. Thereby, it becomes possible to exhibit the effect derived from a phosphorus compound more. More preferably, it is 5-25 mass%, More preferably, it is 15-25 mass%.
液状安定剤はまた、必要に応じて他の成分を更に含んでもよい。他の成分としては、例えば、溶媒、ジベンゾイルメタン等が挙げられる。
ここで、液状安定剤の総量１００質量％に対し、有機酸亜鉛、過塩基性バリウム塩及びリン化合物が占める割合が５０質量％以上であることが好適である。より好ましくは７０質量％以上、更に好ましくは７５質量％以上である。
The liquid stabilizer may further contain other components as required. Examples of other components include a solvent and dibenzoylmethane.
Here, it is preferable that the proportion of the organic acid zinc, the overbased barium salt, and the phosphorus compound is 50% by mass or more with respect to 100% by mass of the total amount of the liquid stabilizer. More preferably, it is 70 mass% or more, More preferably, it is 75 mass% or more.
本発明の樹脂組成物において、液状安定剤の含有量は、塩素含有樹脂１００重量部に対し、１〜１０重量部である。これにより、液状安定剤由来の効果が発揮されて、耐熱性及び熱安定性に優れる成形体を与える樹脂組成物となる。好ましくは２〜９重量部、より好ましくは２．５〜８重量部である。また、液状安定剤に含まれる過塩基性バリウム塩と有機酸亜鉛との合計含有量は、塩素含有樹脂１００重量部に対し１〜８重量部であることが好ましい。より好ましくは１．１〜４重量部、更に好ましくは１．５〜３重量部である。 In the resin composition of the present invention, the content of the liquid stabilizer is 1 to 10 parts by weight with respect to 100 parts by weight of the chlorine-containing resin. Thereby, the effect derived from a liquid stabilizer is exhibited and it becomes a resin composition which gives the molded object which is excellent in heat resistance and heat stability. Preferably it is 2-9 weight part, More preferably, it is 2.5-8 weight part. Moreover, it is preferable that the total content of the overbased barium salt and the organic acid zinc contained in the liquid stabilizer is 1 to 8 parts by weight with respect to 100 parts by weight of the chlorine-containing resin. More preferably, it is 1.1-4 weight part, More preferably, it is 1.5-3 weight part.
３）マルチトール
マルチトールは、市販品を使用することができる。マルチトールは塩素含有樹脂と相溶性が高く、また、融点が塩素含有樹脂との通常の混練温度よりも低いため、添加しても塩素含有樹脂の透明性を損なわないと考えられる。
3) Commercially available maltitol can be used. Maltitol is highly compatible with the chlorine-containing resin and has a melting point lower than the normal kneading temperature with the chlorine-containing resin. Therefore, it is considered that the transparency of the chlorine-containing resin is not impaired even when added.
本発明の樹脂組成物において、マルチトールの含有量は、塩素含有樹脂１００重量部に対し０．０１〜１重量部である。これにより、マルチトール由来の効果が発揮されて、耐熱性及び熱安定性に優れる成形体を与える樹脂組成物となる。好ましくは０．０５〜０．８重量部、より好ましくは０．１〜０．５重量部である。 In the resin composition of the present invention, the content of maltitol is 0.01 to 1 part by weight with respect to 100 parts by weight of the chlorine-containing resin. Thereby, the effect derived from maltitol is exhibited and it becomes the resin composition which gives the molded object which is excellent in heat resistance and heat stability. Preferably it is 0.05-0.8 weight part, More preferably, it is 0.1-0.5 weight part.
４）可塑剤
本発明の樹脂組成物は、必要に応じて可塑剤を更に含んでもよい。可塑剤として特に限定されず、例えば、フタル酸エステル、アジピン酸アルキルエステル、非フタル酸系可塑剤及びエポキシ化植物油からなる群より選択される少なくとも１種であることが好ましい。
4) Plasticizer The resin composition of the present invention may further contain a plasticizer as necessary. It is not specifically limited as a plasticizer, For example, it is preferable that it is at least 1 sort (s) selected from the group which consists of a phthalic acid ester, an adipic acid alkyl ester, a non-phthalic acid type plasticizer, and an epoxidized vegetable oil.
ここで、本発明の樹脂組成物は、上述した通り硬質樹脂組成物として使用した場合にも、透明性及び耐熱性の発揮に加えて、経時による成形体の表面劣化を充分に抑制することができるものである。硬質樹脂組成物として使用する場合、可塑剤は含まない又は含んでも少量であることが好ましいため、本発明の樹脂組成物１００質量％中の可塑剤の含有量は０〜５質量％であることが好ましい。より好ましくは０〜３質量％、更に好ましくは０〜１質量％である。
なお一般には、可塑剤の含有量が少ない樹脂組成物ほど、透明性及び初期着色性が低下することが知られている。だが本発明では、このような技術常識に反して、可塑剤の含有量が上記のような少量であっても又は可塑剤を含まない場合であっても、高度な透明性及び初期着色性を発揮することができる。
Here, even when the resin composition of the present invention is used as a hard resin composition as described above, in addition to exhibiting transparency and heat resistance, the surface deterioration of the molded body over time can be sufficiently suppressed. It can be done. When used as a hard resin composition, since it is preferable that a plasticizer is not contained or is contained in a small amount, the content of the plasticizer in 100% by mass of the resin composition of the present invention is 0 to 5% by mass. Is preferred. More preferably, it is 0-3 mass%, More preferably, it is 0-1 mass%.
In general, it is known that a resin composition having a smaller plasticizer content has lower transparency and initial colorability. However, in the present invention, contrary to such technical common sense, even if the content of the plasticizer is a small amount as described above or no plasticizer is contained, a high degree of transparency and initial colorability are achieved. It can be demonstrated.
５）その他の成分
本発明の樹脂組成物はまた、必要に応じてその他の成分を含んでもよい。例えば、金属石鹸系熱安定剤、加工助剤、強化剤、滑剤、酸化防止剤、着色剤、耐熱助剤、架橋助剤、安定剤等の各種添加剤が挙げられる。この中でも、ハイドロタルサイトやジベンゾイルメタンを更に含むと、耐熱性がより一層向上するため好適である。
5) Other components The resin composition of this invention may also contain other components as needed. For example, various additives such as metal soap heat stabilizers, processing aids, reinforcing agents, lubricants, antioxidants, colorants, heat-resistant aids, crosslinking aids, stabilizers and the like can be mentioned. Among these, it is preferable to further contain hydrotalcite or dibenzoylmethane since the heat resistance is further improved.
各添加剤はそれぞれ特に限定されないが、例えば、金属石鹸系熱安定剤としてはステアリン酸カルシウム、ステアリン酸バリウム、ステアリン酸亜鉛等の脂肪酸金属塩が挙げられる。 Each additive is not particularly limited, and examples of the metal soap heat stabilizer include fatty acid metal salts such as calcium stearate, barium stearate, and zinc stearate.
加工助剤としては、例えば、（メタ）アクリル酸エステル系重合体等のアクリル系加工助剤が挙げられる。アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸２−エチルヘキシル、アクリル酸シクロヘキシル等が挙げられ、メタクリル酸エステルとしては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸２−エチルヘキシル、メタクリル酸シクロヘキシル等が挙げられる。アクリル系加工助剤は、上記のアクリル酸及び／又はそのエステルや、メタクリル酸及び／又はそのエステルそれぞれの単独の重合体であっても２種以上の共重合体であってもよい。重合体の重量平均分子量は２０万〜７００万であることが好ましい。
上記アクリル系加工助剤の市販品としては、例えば、三菱レイヨン社製のメタブレンＰタイプ、カネカ社製のカネエースＰＡシリーズ、ローム・アンド・ハース社製のパラロイドＫシリーズ等が挙げられる。
Examples of the processing aid include acrylic processing aids such as (meth) acrylic acid ester polymers. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and the like. Examples of the methacrylate ester include methyl methacrylate, methacrylic acid. Examples include ethyl, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like. The acrylic processing aid may be a single polymer or a copolymer of two or more of the above acrylic acid and / or its ester, methacrylic acid and / or its ester. The weight average molecular weight of the polymer is preferably 200,000 to 7 million.
Examples of commercially available acrylic processing aids include, for example, Metablene P type manufactured by Mitsubishi Rayon Co., Kaneace PA series manufactured by Kaneka, Paraloid K series manufactured by Rohm and Haas, and the like.
強化剤としては、例えば、ＭＢＳ（メチルメタクリレート−ブタジエンスチレン共重合体）等のブタジエン系強化剤、塩素化ポリエチレン等が挙げられる。 Examples of the reinforcing agent include butadiene-based reinforcing agents such as MBS (methyl methacrylate-butadiene styrene copolymer), chlorinated polyethylene, and the like.
滑剤としては、例えば、流動パラフィン、工業用白色鉱油、合成パラフィン、石油系ワックス、ペトロラタム；無臭軽質炭化水素、シリコーンオルガノポリシロキサン、脂肪酸、脂肪族アルコール高級脂肪酸動物又は植物油脂から得られた脂肪酸及びそれらの脂肪酸を水素添加したもので、炭素数が８〜２２のもの；ヒドロキシステアリン酸等の直鎖脂肪酸；動物、植物油脂又はそれらの脂肪酸エステルを還元又は天然ロウを分解蒸留して得られる炭素数４以上のもの；トリデシルアルコール、ポリグリコールポリエチレングリコール（分子量２００〜９５００のもの）；ポリプロピレングリコール（分子量１０００以上のもの）；ポリオキシプロピレン−ポリオキシエチレン−ブロック重合体（分子量１９００〜９０００のもの）；の他、オレイルパルミトアマイド、ステアリルエルカアマイド、２ステアロアミドエチルステアレート、エチレンビス脂肪酸アマイド、Ｎ，Ｎ’−オレオイルステアリルエチレンジアミン、Ｎ，Ｎ’ −ビス（２ヒドロキシエチル）アルキル（Ｃ１２〜Ｃ１８）アマイド、ＮＮ’ビス（ヒドロキシエチル）ラウロアマイド、Ｎ−アルキル（Ｃ１６〜Ｃ１８）トリメチレンジアミンと反応したオレイン酸脂肪酸ジエタノールアミン、ジ（ヒドロキシエチル）ジエチレントリアミンモノアセテートのジステアリン酸エステル、ステアリン酸ｎ−ブチル水添ロジンメチルエステル、セバチン酸ジブチル＜ｎ−ブチル、イソブチル共＞、セバチン酸ジオクチル＜２エチルヘキシル、ｎ−オクチル共＞、グリセリン脂肪酸エステル、グリセリンラクトステアリル、ペンタエリスリトールのステアリン酸エステル＜モノ、ジ、トリ、テトラ共＞、ソルビタン脂肪酸エステル、ポリエチレングリコールモノステアレート、ポリエチレングリコールジラウレート、ポリエチレングリコールモノオレエート、ポリエチレングリコールジオレエート、ポリエチレングリコールヤシ脂肪酸エステル、ポリエチレングリコールトール油脂肪酸エステル、エタンジオールモンタン酸エステル、１，３ブタンジオールモンタン酸エステル、ジエチレングリコールステアリン酸エステル、プロピレングリコール脂肪酸エステル、トリグリセライド、アマニ油、パーム油、１２−ヒドロオキシステアリン酸のグリセリンエステル、水添魚油、牛脂スパームアセチワックス、モンタンワックス、カルナバワックス、密蝋、木蝋、硬化鯨油ラウリルステアレート、ステアリルステアレートなど一価脂肪族アルコールの脂肪族飽和酸エステル、ラノリン、ステアリン酸亜鉛、ステアリン酸カルシウムなど高級脂肪酸のアルカリ金属、アルカリ土類金属の塩、低分子量ポリエチレン、低分子量ポリプロピレン、酸化ポリエチレン、フッ素系樹脂、ポリ４フッ化エチレン、４フッ化エチレン／６フッ化プロピレン共重合体、ポリ塩化３フッ化エチレン、ポリフッ化ビニル、その他プロピレングリコールアルギネート、ジアルキルケトン、アクリルコポリマー（例えばモンサント社製モダフロー等）が挙げられる。 Examples of the lubricant include liquid paraffin, industrial white mineral oil, synthetic paraffin, petroleum wax, petrolatum; odorless light hydrocarbon, silicone organopolysiloxane, fatty acid, fatty alcohol obtained from higher fatty acid animal or vegetable fat and oil, and Hydrogenated from these fatty acids and having 8 to 22 carbon atoms; linear fatty acids such as hydroxystearic acid; carbon obtained by reducing animal, vegetable oils or their fatty acid esters or decomposing and distilling natural waxes 4 or more; tridecyl alcohol, polyglycol polyethylene glycol (with a molecular weight of 200-9500); polypropylene glycol (with a molecular weight of 1000 or more); polyoxypropylene-polyoxyethylene-block polymer (with a molecular weight of 1900-9000) Other) Rail palmitoamide, stearyl elcaamide, 2 stearamide ethyl stearate, ethylenebis fatty acid amide, N, N′-oleoyl stearylethylenediamine, N, N′-bis (2hydroxyethyl) alkyl (C12-C18) amide , NN'bis (hydroxyethyl) lauroamide, oleic acid fatty acid diethanolamine reacted with N-alkyl (C16-C18) trimethylenediamine, distearic acid ester of di (hydroxyethyl) diethylenetriamine monoacetate, n-butyl hydrogenated rosin stearate Methyl ester, dibutyl sebacate <n-butyl, isobutyl>, dioctyl sebacate <2 ethylhexyl, n-octyl>, glycerin fatty acid ester, glyceractolactearyl Pentaerythritol stearate <mono, di, tri, tetra>, sorbitan fatty acid ester, polyethylene glycol monostearate, polyethylene glycol dilaurate, polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol palm fatty acid ester, polyethylene Glycolitol oil fatty acid ester, ethanediol montanic acid ester, 1,3 butanediol montanic acid ester, diethylene glycol stearic acid ester, propylene glycol fatty acid ester, triglyceride, linseed oil, palm oil, glycerin ester of 12-hydroxystearic acid, water Fish oil, beef tallow palm acetyl wax, montan wax, carnauba wax, beeswax, wood wax, Alkali saturated acid esters of monohydric aliphatic alcohols such as lauryl stearate and stearyl stearate, alkali metals of higher fatty acids such as lanolin, zinc stearate and calcium stearate, salts of alkaline earth metals, low molecular weight polyethylene, low molecular weight Polypropylene, polyethylene oxide, fluorine resin, polytetrafluoroethylene, tetrafluoroethylene / 6-fluoropropylene copolymer, polychloroethylene trifluoride, polyvinyl fluoride, other propylene glycol alginate, dialkyl ketone, acrylic copolymer ( For example, Monsanto Modaflow, etc.).
酸化防止剤としては、例えば、フェノール系酸化防止剤、硫黄系酸化防止剤等が挙げられる。
フェノール系酸化防止剤としては、例えば、２，６−ジ第三ブチル−ｐ−クレゾール、２，６−ジフェニル−４−オクタデシロキシフェノール、ステアリル（３，５−ジ第三ブチル−４−ヒドロキシフェニル）−プロピオネート、ジステアリル（３，５−ジ第三ブチル−４−ヒドロキシベンジル）ホスホネート、チオジエチレングリコールビス〔（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオネート〕、１，６−ヘキサメチレンビス〔（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオネート〕、１，６−ヘキサメチレンビス〔（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオン酸アミド〕、４，４’−チオビス（６−第三ブチル−ｍ−クレゾール）、２，２’−メチレンビス（４−メチル−６−第三ブチルフェノール）、２，２−メチレンビス（４−エチル−６−第三ブチルフェノール）、ビス〔３，３−ビス（４−ヒドロキシ−３−第三ブチルフェニル）ブチリックアシッド〕グリコールエステル、４，４’−ブチリデンビス（６−第三ブチル−ｍ−クレゾール）、２，２’−エチリデンビス（４，６−ジ第三ブチルフェノール）、２，２’−エチリデンビス（４−第二ブチル−６−第三ブチルフェノール）、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−第三ブチルフェニル）ブタン、ビス〔２−第三ブチル−４−メチル−６−（２−ヒドロキシ−３−第三ブチル−５−メチルベンジル）フェニル〕テレフタレート、１，３，５−トリス（２，６−ジメチル−３−ヒドロキシ−４−第三ブチルベンジル）イソシアヌレート、１，３，５−トリス（３，５−ジ第三ブチル−４−ヒドロキシベンジル）イソシアヌレート、１，３，５−トリス（３，５−ジ第三ブチル−４−ヒドロキシベンジル）−２，４，６−トリメチルベンゼン、１，３，５−トリス〔（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオニルオキシエチル〕イソシアヌレート、テトラキス〔メチレン−３−（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオネート〕メタン、２−第三ブチル−４−メチル−６−（２−アクリロイルオキシ−３−第三ブチル−５−メチルベンジル）フェノール、３，９−ビス〔１，１−ジメチル−２−｛（３−第三ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝〕エチル〕−２，４，８，１０−テトラオキサスピロ〔５，５〕ウンデカン、トリエチレングリコールビス〔（３−第三ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート〕等が挙げられる。
Examples of the antioxidant include a phenol-based antioxidant and a sulfur-based antioxidant.
Examples of phenolic antioxidants include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxy). Phenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6- Hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6-tert-butyl) Ruphenol), 2,2-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4 '-Butylidenebis (6-tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert Tributylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3- Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3 5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6- Trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-ditert-butyl-4) -Hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl -2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy}] ethyl] -2,4,8,10-tetraoxaspiro [5,5] un Kang, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.
硫黄系酸化防止剤としては、例えば、チオジプロピオン酸ジラウリル、ジミリスチル、ジステアリル等のジアルキルチオジプロピオネート類及びペンタエリスリトールテトラ（β−ドデシルメルカプトプロピオネート）等のポリオールのβ−アルキルメルカプトプロピオン酸エステル類が挙げられる。 Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl, and β-alkyl mercaptopropion of polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include acid esters.
着色剤としては、例えば、ＴｉＯ２、酸化ジルコニウム、ＢａＳＯ４、酸化亜鉛（亜鉛華）リトポン（硫化亜鉛と硫酸バリウムとの混合物）、カーボンブラック、カーボンブラックと二酸化チタンの混合物、酸化鉄、Ｓｂ２Ｏ３、Ｃｒ２Ｏ３、コバルトブルー、コバルトグリーン等のスピネル、ウルトラマリンブルー等の無機顔料や、アゾ顔料、フタロシアニン顔料、キナクリドン顔料、ペリレン顔料、ジケトピロロピロール顔料、アントラキノン顔料等の有機顔料が挙げられる。更に、上記顔料を複合した複合顔料も挙げられる。 Examples of the colorant include TiO 2 , zirconium oxide, BaSO 4 , zinc oxide (zinc white) lithopone (a mixture of zinc sulfide and barium sulfate), carbon black, a mixture of carbon black and titanium dioxide, iron oxide, and Sb 2. Organic pigments such as inorganic pigments such as spinel such as O 3 , Cr 2 O 3 , cobalt blue and cobalt green, ultramarine blue, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments, anthraquinone pigments Is mentioned. Furthermore, the composite pigment which compounded the said pigment is also mentioned.
耐熱助剤としては、例えば、ハイドロタルサイト、ゼオライト、ジペンタエリスルトールとアジピン酸との部分エステル、ポリオール類及びトリス（２−ヒドロキシエチル）イソシアヌレート等が挙げられる。中でも、本発明の樹脂組成物がハイドロタルサイトを更に含むものであると、耐熱性がより一層向上するため好適である。ハイドロタルサイトの含有量は、塩素含有樹脂１００重量部に対し、０．０１〜５重量部であることが好ましい。より好ましくは０．０５〜３重量部である。 Examples of the heat-resistant auxiliary include hydrotalcite, zeolite, partial ester of dipentaerythritol and adipic acid, polyols, tris (2-hydroxyethyl) isocyanurate, and the like. Among these, it is preferable that the resin composition of the present invention further contains hydrotalcite because the heat resistance is further improved. The hydrotalcite content is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the chlorine-containing resin. More preferably, it is 0.05-3 weight part.
上記樹脂組成物を得る方法は特に限定されず、塩素含有樹脂、液状安定剤、マルチトール及び必要に応じて使用される任意成分を混合すればよい。混合方法も特に限定されず、例えば、ヘンシェルミキサーやスーパーミキサーで混合し、得られた混合物をロール、バンバリーミキサー、押出機等を用いて均一に混練することが好適である。 The method for obtaining the resin composition is not particularly limited, and a chlorine-containing resin, a liquid stabilizer, maltitol, and optional components used as necessary may be mixed. The mixing method is not particularly limited, and for example, it is preferable to mix with a Henschel mixer or a super mixer, and knead the obtained mixture uniformly using a roll, a Banbury mixer, an extruder, or the like.
上記樹脂組成物は、高透明性と高耐熱性とを両立することができ、しかも塩素含有樹脂由来の各種物性に優れる成形品を、外観を低下させることなく与えることができる。それゆえ、成形体用途に特に有用である。 The resin composition can achieve both high transparency and high heat resistance, and can give a molded product excellent in various physical properties derived from a chlorine-containing resin without deteriorating the appearance. Therefore, it is particularly useful for molded body applications.
２、成形体
本発明の成形体は、上述した本発明の塩素含有樹脂組成物を用いてなるものである。すなわち上記塩素含有樹脂組成物の成形体である。それゆえ、耐熱性とともに透明性に特に優れ、耐酸性をも発揮することができる。なお、本発明の樹脂組成物を用いると、成型時のプレートアウトや発泡を充分に抑制することもできるため、得られる成形体は外観も良好で、しかも生産性にも優れることになる。
本発明の成形体は、透明成形体であることが特に好適である。
2. Molded body The molded body of the present invention is formed by using the above-described chlorine-containing resin composition of the present invention. That is, a molded body of the chlorine-containing resin composition. Therefore, it is particularly excellent in transparency as well as heat resistance, and can exhibit acid resistance. When the resin composition of the present invention is used, plate-out and foaming at the time of molding can be sufficiently suppressed, so that the obtained molded article has a good appearance and excellent productivity.
The molded body of the present invention is particularly preferably a transparent molded body.
成形体の形状は特に限定されず、板状、シート状、フィルム状、膜状等の平面形状の他、ひも状、棒状、ペレット状、管状等のその他の形状が挙げられる。中でも、取扱性等の観点から、板状、フィルム状又はシート状であることが好適である。また、成形体として具体的には、各種フィルム、電線、パイプ、樹脂窓枠等が好適である。 The shape of the molded body is not particularly limited, and examples thereof include other shapes such as a string shape, a rod shape, a pellet shape, and a tubular shape in addition to a planar shape such as a plate shape, a sheet shape, a film shape, and a film shape. Among these, from the viewpoint of handleability, a plate shape, a film shape, or a sheet shape is preferable. Further, specifically, various films, electric wires, pipes, resin window frames and the like are suitable as the molded body.
成形（成型とも称す）方法も限定されず、押出成型、射出成型、ロール成形、ディップ成型、ブロー成型等が挙げられる。なお、上記成形体は、押出成型により得られる成形体（押出成型体）であることが好適である。押出成型（押出成形）は、押出成形機を用いて行うことが好ましいが、この方法によれば、各種物性に優れる成形体を作業性よく、容易かつ簡便に、収率良く与えることができる。 The molding (also referred to as molding) method is not limited, and examples thereof include extrusion molding, injection molding, roll molding, dip molding, and blow molding. The molded body is preferably a molded body (extruded molded body) obtained by extrusion molding. Extrusion molding (extrusion molding) is preferably performed using an extrusion molding machine, but according to this method, a molded article having various physical properties can be easily and easily provided with good yield with good workability.
上記成形体（特に、板状、フィルム状又はシート状の成形体）は、２ｍｍ厚での全光線透過率が８５％以上であることが好適である。より好ましくは９０％以上である。また、２ｍｍ厚でのヘイズが４０％以下であることが好ましい。より好ましくは３０％以下、更に好ましくは２０％以下である。 The molded body (particularly, a plate-shaped, film-shaped or sheet-shaped molded body) preferably has a total light transmittance of 85% or more at a thickness of 2 mm. More preferably, it is 90% or more. Moreover, it is preferable that the haze in 2 mm thickness is 40% or less. More preferably, it is 30% or less, More preferably, it is 20% or less.
本明細書中、全光線透過率は、成形体を透過する全ての光の割合であり、ヘイズは、全光線透過光中の拡散透過光の割合である。具体的には、後述する実施例に記載の方法によりヘイズ値を測定することができ、１００％からこのヘイズ値を差し引くことで、全光線透過率を求めることができる。 In the present specification, the total light transmittance is a ratio of all the light transmitted through the molded body, and the haze is a ratio of the diffuse transmitted light in the total light transmitted light. Specifically, the haze value can be measured by the method described in Examples described later, and the total light transmittance can be obtained by subtracting this haze value from 100%.
本発明を詳細に説明するために以下に具体例を挙げるが、本発明はこれらの例のみに限定されるものではない。特に断りのない限り、「部」とは、「重量部（又は重量部）」を意味する。 In order to describe the present invention in detail, specific examples are given below, but the present invention is not limited to these examples. Unless otherwise specified, “parts” means “parts by weight (or parts by weight)”.
実施例１
塩化ビニル樹脂（信越化学工業社製、ＴＫ−７００）１００部に、表１記載の各種添加剤を表１記載の割合で配合、混合し、塩化ビニル樹脂組成物を得た。得られた塩化ビニル樹脂組成物を、ロール表面温度１７０℃に調整した８インチロール機（関西ロール社製）にて５分間混練し、厚さ０．６ｍｍのロールシートを作製した。このシートを用い、以下の評価試験を行った。結果を表１に示す。
Example 1
Various additives listed in Table 1 were blended and mixed in 100 parts of vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., TK-700) at the ratios listed in Table 1 to obtain a vinyl chloride resin composition. The obtained vinyl chloride resin composition was kneaded for 5 minutes with an 8-inch roll machine (manufactured by Kansai Roll Co., Ltd.) adjusted to a roll surface temperature of 170 ° C. to produce a roll sheet having a thickness of 0.6 mm. The following evaluation tests were conducted using this sheet. The results are shown in Table 1.
１）オーブン耐熱性
庫内温度を１９０℃に保持したＥＳＰＥＣ社製ギアオーブンに、実施例１で作成したシートを入れて４０分間保持した。保持する前後のシートを用い、色差計（日本電色工業社製、同時測光方式分光式色差計ＳＱ−２０００）にて色差を測定しΔＥを求めた。このΔＥに基づき、下記基準にて着色性を評価した。なお、ΔＥが小さいほど、色調が良好であり不具合が発生する可能性が低い。
◎：ΔＥが１５以下。
〇：ΔＥが１５を超えて４０以下。
△：ΔＥが４０を超えて６０以下。
×：ΔＥが６０を超える。
1) The sheet prepared in Example 1 was put into a gear oven manufactured by ESPEC having an oven heat-resistant internal temperature maintained at 190 ° C. and held for 40 minutes. Using the sheet before and after holding, the color difference was measured by a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., simultaneous photometry type spectral color difference meter SQ-2000) to obtain ΔE. Based on this ΔE, the colorability was evaluated according to the following criteria. It should be noted that the smaller the ΔE, the better the color tone and the lower the possibility of occurrence of defects.
A: ΔE is 15 or less.
A: ΔE exceeds 15 and is 40 or less.
Δ: ΔE is more than 40 and 60 or less.
X: ΔE exceeds 60
２）プレス耐熱性
プレス表面温度１９０℃のプレス機（東洋精機製作所製、ＭＩＮＩ ＴＥＳＴ ＰＲＥＳＳ−１０）を用い、実施例１で作製したシートを４枚重ねて厚さ２ｍｍになるように、１００ｋｇ／ｃｍ２にて３０分間保持した。保持後のシートについて、上述の色差計にてＹＩ値を測定した。このＹＩに基づき、下記基準にて着色性を評価した。なお、ＹＩ値が小さいほど、色調が良好であり不具合が発生する可能性が低い。
◎：ＹＩが２５以下。
〇：ＹＩが２５を超えて４０以下。
△：ＹＩが４０を超えて４５以下。
×：ＹＩが４５を超える。
2) Press heat resistance Press using a press machine (manufactured by Toyo Seiki Seisakusho, MINI TEST PRESS-10) with a surface temperature of 190 ° C., so that four sheets produced in Example 1 are stacked to a thickness of 2 mm. Hold at cm 2 for 30 minutes. About the sheet | seat after holding | maintenance, YI value was measured with the above-mentioned color difference meter. Based on this YI, the colorability was evaluated according to the following criteria. Note that the smaller the YI value, the better the color tone and the lower the possibility of occurrence of defects.
A: YI is 25 or less.
◯: YI exceeds 25 and is 40 or less.
(Triangle | delta): YI exceeds 40 and is 45 or less.
X: YI exceeds 45.
３）透明性
実施例１で作製したシートを長さ５０ｍｍ×幅５０ｍｍに裁断し、これを４枚重ね合わせ、電熱プレス機（東洋精機製作所製）にて１９０℃×１０分プレスし２ｍｍ厚さの試験片を作成した。この試験片について、日本電色工業社製の測定機器（Ｈａｚｅ Ｍｅｔｅｒ ＮＤＨ４０００）にてヘイズ値を測定した。
3) Transparency The sheet produced in Example 1 was cut into a length of 50 mm and a width of 50 mm, and four of these sheets were stacked, pressed at 190 ° C. for 10 minutes with an electric heating press (manufactured by Toyo Seiki Seisakusho), and 2 mm thick A test piece was prepared. About this test piece, the haze value was measured with the measuring instrument (Haze Meter NDH4000) by Nippon Denshoku Industries Co., Ltd.
４）耐酸性
実施例１で作製したシートを長さ５０ｍｍ×幅５０ｍｍに裁断し、これを４枚重ね合わせ、電熱プレス機（東洋精機製作所製）にて１９０℃×１０分プレスし２ｍｍ厚さの試験片を作成した。実施例１で作製したシートを塩酸に浸漬させ、１週間後の重量変化を測定した。
○：０．０５重量％以下
△：０．１重量％以下
×：０．１重量％超
4) Acid resistance The sheet produced in Example 1 was cut into a length of 50 mm and a width of 50 mm, and four sheets thereof were stacked and pressed at 190 ° C. for 10 minutes with an electric heating press (manufactured by Toyo Seiki Seisakusho) to a thickness of 2 mm. A test piece was prepared. The sheet produced in Example 1 was immersed in hydrochloric acid, and the change in weight after 1 week was measured.
○: 0.05% by weight or less Δ: 0.1% by weight or less ×: More than 0.1% by weight
５）プレートアウト
実施例１にて用いた８インチロール機の、混練後のロール表面について、プレートアウトの有無を目視により観察し、下記基準に基づいて評価した。
○：付着物が確認できなかった。
△：わずかに付着物が確認された。
×：大きな付着物が確認された。
5) Plate-out The presence or absence of plate-out was visually observed on the roll surface after kneading of the 8-inch roll machine used in Example 1, and evaluated based on the following criteria.
○: No deposits could be confirmed.
Δ: Slightly adhered matter was confirmed.
X: A large deposit was confirmed.
６）発泡性
実施例１で作製したシートを長さ５０ｍｍ×幅５０ｍｍに裁断し、これを４枚重ね合わせ、電熱プレス機（東洋精機製作所製）にて１９０℃×１０分プレスし、２ｍｍ厚さの試験片を作成した。得られた試験片表面の発泡性を、目視にて下記基準で評価した。
○：試験片表面又は中に発砲がない。外観不良となるおそれがなく良好であった。
△：試験片表面又は中に１〜５個の発泡がある。
×：試験片表面又は中に５個を超える発泡がある。外観不良となるレベルである。
6) Foamability The sheet produced in Example 1 was cut into a length of 50 mm and a width of 50 mm, and four sheets thereof were stacked, pressed at 190 ° C. for 10 minutes with an electric heating press (manufactured by Toyo Seiki Seisakusho), and 2 mm thick A test specimen was prepared. The foamability of the obtained test piece surface was visually evaluated according to the following criteria.
○: There is no firing on the surface or inside of the test piece. It was good with no risk of poor appearance.
(Triangle | delta): There exist 1-5 foam on the test piece surface or inside.
X: There are more than 5 bubbles on the surface or inside of the test piece. This is a level that results in poor appearance.
実施例２〜７、比較例１〜７
表１、２記載の各種添加剤を当該表記載の割合で用いたこと以外は実施例１と同様にして、塩化ビニル樹脂組成物、ロールシートをそれぞれ作製した。このシートを用い、実施例１と同様に評価試験を行った。結果を表１、２に示す。
Examples 2-7, Comparative Examples 1-7
A vinyl chloride resin composition and a roll sheet were prepared in the same manner as in Example 1 except that the various additives shown in Tables 1 and 2 were used in the proportions shown in the tables. Using this sheet, an evaluation test was conducted in the same manner as in Example 1. The results are shown in Tables 1 and 2.
表１、２中の記号・略号等は、以下の通りである。
塩化ビニル樹脂：ＴＫ−７００（信越化学工業社製）
強化剤：カネエースＢ−５１３（カネカ社製）
加工助剤：カネエースＰＡ−２０（カネカ社製）、及び、メタブレンＰ−７００（三菱レイヨン社製）
滑剤：リケマールＳ−１００（理研ビタミン社製）、リケマールＳＬ−０２（理研ビタミン社製）、及び、ロキシオールＧ−７８（コグニスシャパン社製）
過塩基性バリウム塩：ＰＳ−２５１３（プラスチスタブ２５１３）（ＡＭスタビライザーズ社製）
リン化合物：ジフェニルイソオクチルフォスファイト（ＯＤＰＰ、城北化学社製）、及び、ジフェニルトリデシルフォスファイト（ＰＸ−２５７、共同薬品社製）
溶媒：ＢＤＧ（ダウ・ケミカル社製）及びフォグソルベント（ＪＸエネルギー社製）
マルチトール：アマルティＭＲ−１００、三菱商事フードテック社製
ハイドロタルサイト：ＳＴＡＢＩＡＣＥ ＨＴ−７（堺化学工業社製）
ＤＢＭ：ジベンゾイルメタン（ロディア社製）
Ｂａ／Ｚｎ系安定剤（粉状）：ラウリン酸バリウム（Ｂ−１２、堺化学工業社製）と、ラウリン酸亜鉛（ＬＺ−Ｐ、堺化学工業社製）との混合物
Ｃａ／Ｚｎ系安定剤（粉状）：ラウリン酸亜鉛（堺化学工業社製）とＺｎ変性ハイドロタルサイト（堺化学工業社製）との混合物
ソルビトール：物産フードサイエンス社製
マンニトール：物産フードサイエンス社製
ラクチトール：物産フードサイエンス社製
The symbols and abbreviations in Tables 1 and 2 are as follows.
Vinyl chloride resin: TK-700 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Reinforcing agent: Kane Ace B-513 (manufactured by Kaneka)
Processing aids: Kane Ace PA-20 (manufactured by Kaneka) and Metabrene P-700 (manufactured by Mitsubishi Rayon)
Lubricant: Riquemar S-100 (manufactured by Riken Vitamin Company), Riquemar SL-02 (manufactured by Riken Vitamin Company), and Roxyol G-78 (manufactured by Cognis Chapan)
Overbased barium salt: PS-2513 (plastic stub 2513) (manufactured by AM Stabilizers)
Phosphorus compounds: diphenylisooctyl phosphite (ODPP, manufactured by Johoku Chemical Co., Ltd.) and diphenyl tridecyl phosphite (PX-257, manufactured by Kyodo Yakuhin Co., Ltd.)
Solvent: BDG (manufactured by Dow Chemical) and fog solvent (manufactured by JX Energy)
Maltitol: Amarty MR-100, Mitsubishi Corporation Foodtech Hydrotalcite: STABIACE HT-7 (manufactured by Sakai Chemical Industry Co., Ltd.)
DBM: Dibenzoylmethane (manufactured by Rhodia)
Ba / Zn stabilizer (powder): a mixture of barium laurate (B-12, manufactured by Sakai Chemical Industry Co., Ltd.) and zinc laurate (LZ-P, manufactured by Sakai Chemical Industry Co., Ltd.) Ca / Zn stabilizer (Powder): Zinc laurate (manufactured by Sakai Chemical Industry Co., Ltd.) and Zn-modified hydrotalcite (manufactured by Sakai Chemical Industry Co., Ltd.) Made by company
上記表１、２により、以下の事項を確認した。
実施例１〜７は、塩素含有樹脂に対し、過塩基性バリウム塩及び有機酸亜鉛を含む液状安定剤とマルチトールとをそれぞれ所定量含む本発明の樹脂組成物を使用した例である。これに対し、比較例１はマルチトールを含まない点で、比較例２はマルチトールの代わりにソルビトールを使用した点で、比較例３〜５は液状安定剤ではなく従来の粉状安定剤（Ｂａ／Ｚｎ系安定剤又はＣａ／Ｚｎ系安定剤）を使用した点で、比較例６〜７はマルチトールの代わりに各々ラクチトール、マンニトールを使用した点で、実施例１〜７とは相違する。この相違の下、耐熱性及び透明性を評価した結果を対比すると、実施例１〜７では、比較例１〜７に比較して耐熱性及び透明性のいずれか１以上の物性が著しく高いことが分かる。実施例１〜７で得た樹脂組成物はまた、比較例１〜７に比較して成形体の耐酸性も良好で、プレートアウト抑制能や発泡抑制能も有していた。
従って、塩素含有樹脂に対し、過塩基性バリウム塩及び有機酸亜鉛を含む液状安定剤とマルチトールとを所定量含む構成の樹脂組成物であることによって、透明性及び耐熱性に加え、耐酸性にも優れる成形品を、発泡やプレートアウト発生を充分に抑制しながら生産性良く与えることができることが分かった。
The following items were confirmed from Tables 1 and 2 above.
Examples 1 to 7 are examples in which the resin composition of the present invention containing a predetermined amount of a liquid stabilizer containing an overbased barium salt and an organic acid zinc and maltitol is used for the chlorine-containing resin. In contrast, Comparative Example 1 does not contain maltitol, Comparative Example 2 uses sorbitol instead of maltitol, and Comparative Examples 3 to 5 are not powder stabilizers but conventional powder stabilizers ( Comparative Examples 6 to 7 are different from Examples 1 to 7 in that lactitol and mannitol were used instead of maltitol in that Ba / Zn-based stabilizer or Ca / Zn-based stabilizer) was used. . Under these differences, the results of evaluating heat resistance and transparency are compared, and in Examples 1 to 7, the physical properties of either one or more of heat resistance and transparency are significantly higher than those of Comparative Examples 1 to 7. I understand. The resin compositions obtained in Examples 1 to 7 also had good acid resistance of the molded bodies as compared with Comparative Examples 1 to 7, and had plate-out inhibiting ability and foam inhibiting ability.
Therefore, in addition to transparency and heat resistance, in addition to transparency and heat resistance, the resin composition has a liquid stabilizer containing overbased barium salt and organic acid zinc and maltitol for chlorine-containing resin. It was also found that a molded product excellent in productivity can be given with good productivity while sufficiently suppressing foaming and plate-out occurrence.
Claims (5)
過塩基性バリウム塩及び有機酸亜鉛を含む液状安定剤１〜１０重量部と、
マルチトール０．０１〜１重量部とを含む
ことを特徴とする塩素含有樹脂組成物。 For 100 parts by weight of chlorine-containing resin,
1 to 10 parts by weight of a liquid stabilizer comprising an overbased barium salt and an organic acid zinc;
A chlorine-containing resin composition comprising 0.01 to 1 part by weight of maltitol.
ことを特徴とする請求項１に記載の塩素含有樹脂組成物。 Content of the plasticizer in the said chlorine containing resin composition is 0-5 mass% with respect to 100 mass% of chlorine containing resin compositions, The chlorine containing resin composition of Claim 1 characterized by the above-mentioned.
ことを特徴とする成形体。 A molded product comprising the chlorine-containing resin composition according to claim 1.
ことを特徴とする請求項３に記載の成形体。 It is a transparent molded object, The molded object of Claim 3 characterized by the above-mentioned.
ことを特徴とする請求項３又は４に記載の成形体。 It is plate shape, film shape, or sheet shape, The molded object of Claim 3 or 4 characterized by the above-mentioned.
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| WO2012014583A1 (en) * | 2010-07-29 | 2012-02-02 | 株式会社Adeka | Vinyl-chloride-based resin composition for transparent product |
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| CN103756455B (en) * | 2014-01-14 | 2016-05-18 | 北京天山新材料技术有限公司 | A kind of high temperature resistant peelable protective finish and preparation method thereof |
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| JPH0459850A (en) * | 1990-06-29 | 1992-02-26 | Asahi Denka Kogyo Kk | Polyvinyl chloride-based resin composition for food packaging |
| JPH08283498A (en) * | 1995-04-17 | 1996-10-29 | Ciba Geigy Ag | Stabilized halogenated polymer |
| JP2004175868A (en) * | 2002-11-26 | 2004-06-24 | Dainippon Ink & Chem Inc | Halogen-containing resin composition |
| JP2004238364A (en) * | 2003-02-07 | 2004-08-26 | Asahi Denka Kogyo Kk | Liquid perbasic metal complex and method for producing the same |
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| WO2011024399A1 (en) * | 2009-08-24 | 2011-03-03 | 株式会社Adeka | Vinyl chloride resin composition for transparent products |
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| TW201837099A (en) | 2018-10-16 |
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