JP2022162603A - Paste vinyl chloride-based resin composition - Google Patents
Paste vinyl chloride-based resin composition Download PDFInfo
- Publication number
- JP2022162603A JP2022162603A JP2021067488A JP2021067488A JP2022162603A JP 2022162603 A JP2022162603 A JP 2022162603A JP 2021067488 A JP2021067488 A JP 2021067488A JP 2021067488 A JP2021067488 A JP 2021067488A JP 2022162603 A JP2022162603 A JP 2022162603A
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- JP
- Japan
- Prior art keywords
- weight
- parts
- vinyl chloride
- paste
- chloride resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 67
- 229920005989 resin Polymers 0.000 claims abstract description 67
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 51
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 35
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 35
- 239000003381 stabilizer Substances 0.000 claims abstract description 26
- 239000006260 foam Substances 0.000 claims abstract description 24
- 239000004014 plasticizer Substances 0.000 claims abstract description 23
- 239000004088 foaming agent Substances 0.000 claims abstract description 19
- 239000000049 pigment Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 13
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 25
- 239000004156 Azodicarbonamide Substances 0.000 claims description 6
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical group NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 6
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 2
- 238000005187 foaming Methods 0.000 abstract description 7
- 150000004996 alkyl benzenes Chemical class 0.000 abstract description 2
- 229940077388 benzenesulfonate Drugs 0.000 abstract description 2
- 238000010097 foam moulding Methods 0.000 abstract 1
- 239000004816 latex Substances 0.000 description 27
- 229920000126 latex Polymers 0.000 description 27
- 239000000178 monomer Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 13
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 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 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 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
- 229910052725 zinc Inorganic materials 0.000 description 2
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical class FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- IOSXLUZXMXORMX-UHFFFAOYSA-N 1-ethenoxypentane Chemical compound CCCCCOC=C IOSXLUZXMXORMX-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- JHWLWOYSFJIYQV-UHFFFAOYSA-N 4-dodecylbenzenesulfonate;tris(2-hydroxyethyl)azanium Chemical compound OCC[NH+](CCO)CCO.CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHWLWOYSFJIYQV-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical class CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 description 1
- FVAIEHAPKZFAGH-UHFFFAOYSA-N 6,6-dimethylheptanoyl 6,6-dimethylheptaneperoxoate Chemical compound CC(CCCCC(=O)OOC(CCCCC(C)(C)C)=O)(C)C FVAIEHAPKZFAGH-UHFFFAOYSA-N 0.000 description 1
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical class CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229940056585 ammonium laurate Drugs 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- VJCJAQSLASCYAW-UHFFFAOYSA-N azane;dodecanoic acid Chemical compound [NH4+].CCCCCCCCCCCC([O-])=O VJCJAQSLASCYAW-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000006084 composite stabilizer Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- RZMWTGFSAMRLQH-UHFFFAOYSA-L disodium;2,2-dihexyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCC RZMWTGFSAMRLQH-UHFFFAOYSA-L 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- CFNDRVCFJKQSHT-UHFFFAOYSA-N dodecyl benzenesulfonate;potassium Chemical compound [K].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 CFNDRVCFJKQSHT-UHFFFAOYSA-N 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- ZQZUENMXBZVXIZ-UHFFFAOYSA-N ethenyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC=C ZQZUENMXBZVXIZ-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
- XPNLOZNCOBKRNJ-UHFFFAOYSA-N ethyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C=C.COC(=O)C(C)=C XPNLOZNCOBKRNJ-UHFFFAOYSA-N 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000000216 gellan gum Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 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
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- MWCRSWMJQSTWMA-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;octyl prop-2-enoate Chemical compound COC(=O)C(C)=C.CCCCCCCCOC(=O)C=C MWCRSWMJQSTWMA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- XNTUJOTWIMFEQS-UHFFFAOYSA-N octadecanoyl octadecaneperoxoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCCCCCCCC XNTUJOTWIMFEQS-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Chemical class 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- URLJMZWTXZTZRR-UHFFFAOYSA-N sodium myristyl sulfate Chemical compound CCCCCCCCCCCCCCOS(O)(=O)=O URLJMZWTXZTZRR-UHFFFAOYSA-N 0.000 description 1
- 229950005425 sodium myristyl sulfate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、表面強度、伸び、発泡性、表面平滑性に優れ、特に発泡壁紙用として優れた特性を有するペースト塩化ビニル系樹脂組成物に関するものである。 TECHNICAL FIELD The present invention relates to a paste vinyl chloride-based resin composition which is excellent in surface strength, elongation, foamability and surface smoothness, and which is particularly suitable for use in foamed wallpaper.
ペースト加工用であるペースト塩化ビニル系樹脂（以下、ペースト塩ビと略記する場合もある。）は、一般に可塑剤、充填剤、安定剤又はその他の配合剤などと共に混練することにより、ペースト塩ビ組成物ゾルを調製し、該ペースト塩ビ組成物ゾルを使用し種々の成形加工法により壁紙、タイルカーペット、手袋などの様々な成形加工品に用いられている。 Paste vinyl chloride resin for paste processing (hereinafter sometimes abbreviated as paste vinyl chloride) is generally kneaded with a plasticizer, a filler, a stabilizer, or other compounding agents to form a paste vinyl chloride composition. A sol is prepared, and the paste vinyl chloride composition sol is used for various molded products such as wallpaper, tile carpet, and gloves by various molding methods.
そして、壁紙用途分野においては、壁紙施工職人の人手不足や高齢化が課題となり、施工の容易な壁装材が求められている。このため、例えば、壁紙用裏打紙と樹脂層を備える壁装材においては、一般的に、製品重量が軽く取り扱いが容易な製品が好まれる。また、施工する下地の凹凸を隠蔽するために、発泡剤を用いてその厚さを厚くしたものが非常に多い。 In the wallpaper application field, labor shortage and aging of wallpaper construction craftsmen have become issues, and wall covering materials that are easy to install are required. For this reason, for wallcovering materials comprising a wallpaper backing paper and a resin layer, for example, products that are light in product weight and easy to handle are generally preferred. In addition, in order to hide the unevenness of the base to be constructed, many of them are thickened by using a foaming agent.
しかしながら、発泡剤を用いて壁紙を厚くすると、壁紙の表面強度が低下し、施工時や施工後の生活における破損のリスクが高まることがある。 However, when a foaming agent is used to thicken the wallpaper, the surface strength of the wallpaper is lowered, and the risk of breakage during construction and after construction may increase.
この課題を解決するために、例えば、高い表面強度と必要十分な厚みを備えつつ軽量化した発泡壁紙及びその製造方法が提案されている（例えば特許文献１参照。）。 In order to solve this problem, for example, a lightweight foamed wallpaper having a high surface strength and a necessary and sufficient thickness and a method for producing the same have been proposed (see, for example, Patent Document 1).
しかし、特許文献１に提案の発泡壁紙においては、発泡壁紙用としての塩化ビニル系樹脂組成物については何ら検討のなされていないものであった。 However, in the foamed wallpaper proposed in Patent Document 1, no consideration has been given to vinyl chloride-based resin compositions for foamed wallpaper.
そこで、本発明は、高い表面強度、表面平滑性と発泡性を備え、特に発泡壁紙用として適したペースト塩ビ組成物及びそれよりなる発泡体を提供することにある。 Accordingly, an object of the present invention is to provide a paste vinyl chloride composition that has high surface strength, surface smoothness and foamability, and is particularly suitable for foamed wallpaper, and a foam comprising the same.
本発明者は、上記の課題について鋭意検討を重ねた結果、塩化ビニル系樹脂に特定量のアクリル系樹脂及びアルキルベンゼンスルホン酸塩を含むペースト塩ビに対して、特定量の可塑剤、充填剤、顔料、安定剤、発泡剤、減粘剤を含むペースト塩ビ組成物が、極めて表面強度が高く、発泡性の良好なものとなることを見出し、本発明を完成させるに至った。 As a result of intensive studies on the above problems, the present inventors have found that a paste vinyl chloride containing a specific amount of acrylic resin and alkylbenzene sulfonate in vinyl chloride resin has a specific amount of plasticizer, filler, and pigment. , a stabilizer, a foaming agent, and a viscosity reducing agent, and found that the paste vinyl chloride composition has extremely high surface strength and good foamability, leading to the completion of the present invention.
即ち、本発明は、重合度１２００以上２２００以下の塩化ビニル系樹脂１００重量部に対して、アクリル系樹脂を０．１重量部を超えて５重量部以下、アルキルベンゼンスルホン酸塩０．０５重量部以上２．５重量部以下を含むペースト塩化ビニル系樹脂１００重量部に対し、可塑剤２０重量部以上７０重量部以下、充填剤５０重量部以下、顔料１０重量部以上３０重量部以下、安定剤１重量部以上４．５重量部以下、発泡剤１重量部以上４．５重量部以下、減粘剤１重量部以上３０重量部以下を含むものであることを特徴とするペースト塩化ビニル系樹脂組成物に関するものである。 That is, in the present invention, more than 0.1 parts by weight and 5 parts by weight or less of an acrylic resin and 0.05 parts by weight of an alkylbenzene sulfonate are added to 100 parts by weight of a vinyl chloride resin having a degree of polymerization of 1200 or more and 2200 or less. 20 parts by weight or more and 70 parts by weight or less of a plasticizer, 50 parts by weight or less of a filler, 10 parts by weight or more and 30 parts by weight or less of a pigment, and a stabilizer for 100 parts by weight of a paste vinyl chloride resin containing 2.5 parts by weight or less of the above. 1 part by weight or more and 4.5 parts by weight or less, 1 part by weight or more and 4.5 parts by weight or less of a foaming agent, and 1 part by weight or more and 30 parts by weight or less of a viscosity reducing agent. It is about.
以下、本発明に関し詳細に説明する。 The present invention will be described in detail below.
本発明のペースト塩ビ組成物を構成するペースト塩ビは、塩化ビニル系樹脂１００重量部に対して、アクリル系樹脂を０．１重量部を超えて５重量部以下、アルキルベンゼンスルホン酸塩０．０５重量部以上２．５重量部以下を含むものである。そして、該塩化ビニル系樹脂は、重合度が１２００以上２２００以下ものであり、特に表面強度と表面平滑性に優れるものを提供することが可能なペースト塩ビ組成物となることから重合度１２００以上１８００以下ものであることが好ましく、更に重合度１３００以上１７００以下のものであることが好ましい。ここで、重合度が１２００未満である場合、表面強度に劣るものとなる。一方、重合度が２２００を越えるものである場合、表面平滑性に劣るものとなる。なお、塩化ビニル系樹脂の重合度の測定方法としては、例えばＪＩＳ Ｋ６７２１のウベローデ粘度計を用いて、溶液粘度測定法により重合度として算出する方法を挙げることができる。 The paste vinyl chloride constituting the paste vinyl chloride composition of the present invention contains more than 0.1 parts by weight and 5 parts by weight or less of an acrylic resin and 0.05 parts by weight of an alkylbenzene sulfonate with respect to 100 parts by weight of a vinyl chloride resin. part or more and 2.5 parts by weight or less. The vinyl chloride-based resin has a polymerization degree of 1200 or more and 2200 or less, and it becomes a paste vinyl chloride composition that can provide particularly excellent surface strength and surface smoothness. It is preferably the following, and more preferably has a degree of polymerization of 1300 or more and 1700 or less. Here, when the degree of polymerization is less than 1200, the surface strength is inferior. On the other hand, if the degree of polymerization exceeds 2200, the surface smoothness will be poor. As a method for measuring the degree of polymerization of the vinyl chloride resin, for example, a method of calculating the degree of polymerization by a solution viscosity measurement method using an Ubbelohde viscometer according to JIS K6721 can be mentioned.
該塩化ビニル系樹脂としては、塩化ビニル単独重合体はもとより、共重合体であってもよくその際の共重合可能な単量体としては、例えば酢酸ビニル、プロピオン酸ビニル、ミリスチン酸ビニル、安息香酸ビニル等のビニルエステル類；アクリル酸、メタクリル酸、マレイン酸、フマル酸等の不飽和カルボン酸またはその無水物；アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル等のアクリル酸エステル類；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル等のメタクリル酸エステル類；マレイン酸エステル、フマル酸エステル、桂皮酸エステル類等の不飽和カルボン酸エステル類；ビニルメチルエーテル、ビニルアミルエーテル、ビニルフェニルエーテル等のビニルエーテル類；エチレン、プロピレン、ブテン、ペンテン等のモノオレフィン類；塩化ビニリデン、スチレン及びその誘導体、アクリロニトリル、メタクリロニトリル等を挙げることができる。 The vinyl chloride resin may be a vinyl chloride homopolymer or a copolymer. Examples of copolymerizable monomers include vinyl acetate, vinyl propionate, vinyl myristate, and benzoin. Vinyl esters such as vinyl acid; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid or their anhydrides; acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylic acid methacrylic acid esters such as methyl, ethyl methacrylate and butyl methacrylate; unsaturated carboxylic acid esters such as maleic acid esters, fumaric acid esters and cinnamic acid esters; vinyl methyl ether, vinyl amyl ether, vinyl phenyl ether and the like. vinyl ethers; monoolefins such as ethylene, propylene, butene and pentene; vinylidene chloride, styrene and derivatives thereof, acrylonitrile, methacrylonitrile and the like.
該塩化ビニル系樹脂は、ペースト塩ビの一般的な重合法として知られている乳化重合法、ミクロ懸濁重合法、シード乳化重合法、シードミクロ懸濁重合法等により得られる塩化ビニル系樹脂であってもよく、これら重合法により塩化ビニル系樹脂ラテックスを得て、得られたラテックスの水分を除去することにより得ることができる。その際に、塩化ビニル系樹脂ラテックスから水分を除去する方法としては、例えば噴霧乾燥、流動層乾燥、通気乾燥、回転乾燥、伝導加熱乾燥による方法等が挙げられ、中でも、効率よく水分を除去できることから、噴霧乾燥による方法が好ましい。 The vinyl chloride-based resin is a vinyl chloride-based resin obtained by an emulsion polymerization method, a microsuspension polymerization method, a seed emulsion polymerization method, a seed microsuspension polymerization method, or the like, which are known as general polymerization methods for paste vinyl chloride. It can be obtained by obtaining a vinyl chloride resin latex by these polymerization methods and removing water from the resulting latex. At that time, the method for removing water from the vinyl chloride resin latex includes, for example, spray drying, fluidized bed drying, aeration drying, rotary drying, conduction heating drying, etc. Among them, water should be efficiently removed. Therefore, the spray drying method is preferred.
以下に、該塩化ビニル系樹脂、塩化ビニル系樹脂ラテックスを製造する際の一例として、シードミクロ懸濁重合法による方法を示す。 As an example of the production of the vinyl chloride resin and vinyl chloride resin latex, a seed microsuspension polymerization method is shown below.
シードミクロ懸濁重合法とは、１）ミクロ懸濁重合法により油溶性重合開始剤を含む塩化ビニル系樹脂を含有する塩化ビニル系樹脂シードラテックスを得る第一段階、２）得られたシードラテックスを塩化ビニルモノマー、又は塩化ビニルモノマーとこれと共重合可能な単量体を、脱イオン水、乳化剤、緩衝剤、必要に応じて高級アルコール等の乳化助剤の存在下で緩やかな攪拌で重合を行い、シードラテックスを肥大化させて塩化ビニル系樹脂ラテックスを得る第二段階からなる重合方法である。 The seed microsuspension polymerization method includes 1) the first step of obtaining a vinyl chloride resin seed latex containing a vinyl chloride resin containing an oil-soluble polymerization initiator by the microsuspension polymerization method, and 2) the obtained seed latex. A vinyl chloride monomer, or a vinyl chloride monomer and a monomer copolymerizable therewith, are polymerized with gentle stirring in the presence of deionized water, an emulsifier, a buffer, and, if necessary, an emulsifying aid such as a higher alcohol. and enlarging the seed latex to obtain a vinyl chloride resin latex.
ここで、塩化ビニルモノマーと共重合可能な単量体としては、上記した単量体を例示することができる。また、乳化剤としては、後述するアルキルベンゼンスルホン酸塩以外に、例えばラウリル硫酸エステルナトリウム塩、ミリスチル硫酸エステル塩等のアルキル硫酸エステル塩類；ジオクチルスルホコハク酸ナトリウム塩、ジヘキシルスルホコハク酸ナトリウム塩等のスルホコハク酸塩類；ラウリン酸アンモニウム塩、ステアリン酸カリウム塩等の脂肪酸塩類；ポリオキシエチレンアルキル硫酸エステル塩類、ポリオキシエチレンアルキルアリール硫酸エステル塩類等のアニオン系乳化剤，ソルビタンモノオレート、ポリオキシエチレンソルビタンモノステアレート等のソルビタンエステル類；ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンアルキルエステル類等のノニオン系乳化剤等の従来より知られているものを１種類又は２種類以上用いることができる。緩衝剤としては、例えばリン酸一水素アルカリ金属塩、リン酸二水素アルカリ金属塩、フタル酸水素カリウム、炭酸水素ナトリウム、ホウ酸－苛性カリウム溶液等が挙げられる。 Here, the above-described monomers can be exemplified as the monomer copolymerizable with the vinyl chloride monomer. Examples of emulsifiers other than alkylbenzenesulfonates described later include alkyl sulfate salts such as sodium lauryl sulfate and myristyl sulfate; sulfosuccinates such as sodium dioctylsulfosuccinate and sodium dihexylsulfosuccinate; Fatty acid salts such as ammonium laurate and potassium stearate; anionic emulsifiers such as polyoxyethylene alkyl sulfates and polyoxyethylene alkylaryl sulfates; sorbitans such as sorbitan monooleate and polyoxyethylene sorbitan monostearate Esters: One or more of conventionally known nonionic emulsifiers such as polyoxyethylene alkylphenyl ethers and polyoxyethylene alkyl esters can be used. Examples of buffering agents include alkali metal monohydrogen phosphate, alkali metal dihydrogen phosphate, potassium hydrogen phthalate, sodium hydrogen carbonate, boric acid-caustic potassium solution and the like.
さらに、必要に応じて用いられる乳化助剤としては、例えばセチルアルコール、ラウリルアルコール等の高級アルコール；ラウリン酸、パルミチン酸、ステアリン酸等の高級脂肪酸、そのエステル；芳香族炭化水素、高級脂肪酸炭化水素、塩素化パラフィンのようなハロゲン化炭化水素等が挙げられる。 Furthermore, emulsifying aids used as necessary include, for example, higher alcohols such as cetyl alcohol and lauryl alcohol; higher fatty acids such as lauric acid, palmitic acid and stearic acid, esters thereof; aromatic hydrocarbons and higher fatty acid hydrocarbons. , halogenated hydrocarbons such as chlorinated paraffins, and the like.
また、シードミクロ懸濁重合法に用いられる塩化ビニル系樹脂シードラテックスは、以下のようなミクロ懸濁重合法で調製することが可能である。まず、塩化ビニルモノマー、油溶性重合開始剤、界面活性剤、緩衝剤、高級アルコール、高級脂肪酸、高級脂肪酸エステル、塩素化パラフィン等の分散助剤、必要に応じて重合度調整剤を添加してプレミックスし、ホモジナイザーにより均質化処理して油滴の調整を行なう。この際のホモジナイザーとしては、例えば、コロイドミル、振動攪拌機、二段式高圧ポンプ等を用いることができる。そして、均質化処理した液を重合器に送り、緩やかに攪拌しながら重合器内の温度を上げて重合反応を開始し、所定の転化率に達するまで重合を行なうことにより油溶性重合開始剤を含有する塩化ビニル系樹脂シードラテックスを調整することが可能である。 Also, the vinyl chloride resin seed latex used in the seed microsuspension polymerization method can be prepared by the following microsuspension polymerization method. First, vinyl chloride monomers, oil-soluble polymerization initiators, surfactants, buffers, higher alcohols, higher fatty acids, higher fatty acid esters, dispersing aids such as chlorinated paraffin, and, if necessary, polymerization degree adjusters are added. The oil droplets are adjusted by premixing and homogenizing with a homogenizer. As a homogenizer at this time, for example, a colloid mill, a vibration stirrer, a two-stage high-pressure pump, or the like can be used. Then, the homogenized liquid is sent to the polymerization vessel, and the temperature inside the polymerization vessel is raised while gently stirring to initiate the polymerization reaction. It is possible to adjust the contained vinyl chloride resin seed latex.
その際の油溶性重合開始剤としては、１０時間半減期温度３０～７０℃のジアシルパーオキサイドが好ましく、そのような油溶性重合開始剤としては、例えばイソブチリルパーオキサイド、３，３，５－トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、ラウロイルパーオキサイド、ステアロイルパーオキサイド、コハク酸パーオキサイド等が挙げられる。 As the oil-soluble polymerization initiator at that time, diacyl peroxide having a 10-hour half-life temperature of 30 to 70° C. is preferable. trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide and the like.
該ペースト塩ビを構成するアクリル系樹脂としては、アクリル系樹脂の範疇に属するものであれば如何なるものであってもよく、例えばポリメチルメタクリレート、ポリ（メチルメタクリレート－アクリル酸ブチル）共重合体、ポリ（メチルメタクリレート－アクリル酸エチル）共重合体、ポリ（メチルメタクリレート－アクリル酸オクチル）共重合体等を挙げることができ、中でも高表面強度と発泡性のバランスに優れるペースト塩ビとなることから、ガラス転移温度（Ｔｇ）が、－４０℃～５０℃のアクリル系樹脂であることが好ましく、特に重量平均分子量が５００００～２０００００のアクリル系樹脂であることが好ましい。なお、この際の重量平均分子量は、例えばゲル・パーミエイション・クロマトグラフにより、標準ポリスチレン換算値として求めることができる。また、該アクリル系樹脂は、後述する水性アクリル樹脂エマルションを構成するアクリル系樹脂であってもよい。さらに、増粘型水性アクリル樹脂エマルションを構成するアクリル系樹脂であることが好ましい。 The acrylic resin constituting the paste vinyl chloride may be any resin as long as it belongs to the category of acrylic resins, such as polymethyl methacrylate, poly(methyl methacrylate-butyl acrylate) copolymer, poly (methyl methacrylate-ethyl acrylate) copolymer, poly (methyl methacrylate-octyl acrylate) copolymer, etc., and among them, it is a paste vinyl chloride that has an excellent balance between high surface strength and foamability, so glass An acrylic resin having a transition temperature (Tg) of −40° C. to 50° C. is preferred, and an acrylic resin having a weight average molecular weight of 50,000 to 200,000 is particularly preferred. The weight average molecular weight at this time can be obtained as a standard polystyrene conversion value by gel permeation chromatography, for example. Further, the acrylic resin may be an acrylic resin that constitutes an aqueous acrylic resin emulsion to be described later. Furthermore, it is preferably an acrylic resin that constitutes a thickened water-based acrylic resin emulsion.
該アクリル系樹脂は、特に発泡性と表面強度に優れるものとなることから平均粒径５０ｎｍ以上１０００ｎｍ以下のものであることが好ましく、さらに１００ｎｍ以上４００ｎｍ以下のものが好ましい。この際の平均粒径の測定方法としては、例えばレーザー回折式粒度分布測定や電子顕微鏡観察の結果より算出する方法を挙げることができる。 Since the acrylic resin is particularly excellent in foamability and surface strength, it preferably has an average particle size of 50 nm or more and 1000 nm or less, more preferably 100 nm or more and 400 nm or less. Examples of the method for measuring the average particle diameter at this time include a method of calculating from the results of laser diffraction particle size distribution measurement and electron microscope observation.
そして、該ペースト塩ビは、アクリル系樹脂０．１重量部を超えて５重量部以下を含むものであり、特に発泡性と表面平滑性に優れるものとなることから０．３重量部以上３重量部以下であることが好ましく、更に０．８重量部以上１．５重量部以下であることが好ましい。ここで、０．１重量部以下である場合、表面平滑性に劣るものとなる。一方、５重量部を超える場合、ゾルにした際の粘度が高くなるため、ハンドリング性に課題を発生する場合がある。 The paste vinyl chloride contains more than 0.1 parts by weight and 5 parts by weight or less of an acrylic resin, and is particularly excellent in foamability and surface smoothness, so 0.3 parts by weight or more and 3 parts by weight It is preferably 0.8 parts by weight or more and 1.5 parts by weight or less. Here, when it is 0.1 part by weight or less, the surface smoothness is inferior. On the other hand, if it exceeds 5 parts by weight, the viscosity of the sol becomes high, which may cause problems in handling.
該ペースト塩ビを構成するアルキルベンゼンスルホン酸塩としては、アルキルベンゼンスルホン酸塩の範疇に属するものであれば如何なるものであってもよく、例えばドデシルベンゼンスルホン酸ナトリウム塩、ドデシルベンゼンスルホン酸カリウム塩、ドデシルベンゼンスルホン酸アンモニウム塩、ドデシルベンゼンスルホン酸トリエタノールアンモニウム塩等を挙げることができ、中でも表面平滑性に優れるペースト塩ビを提供することが可能となることからドデシルベンゼンスルホン酸ナトリウム塩であることが好ましい。 As the alkylbenzenesulfonate constituting the paste vinyl chloride, any one belonging to the category of alkylbenzenesulfonates may be used, for example, dodecylbenzenesulfonate sodium salt, dodecylbenzenesulfonate potassium salt, dodecylbenzene Examples thereof include ammonium sulfonate and triethanolammonium dodecylbenzenesulfonate. Among them, sodium dodecylbenzenesulfonate is preferred because it enables the provision of paste vinyl chloride having excellent surface smoothness.
該ペースト塩ビは、アルキルベンゼンスルホン酸塩０．０５重量部以上２．５重量部以下を含むものであり、特に表面平滑性、表面強度に優れるものとなることから０．５重量部以上２．０重量部以下であることが好ましく、更に０．８重量部以上１．５重量部以下を含むものであることが好ましい。そして、該アルキルベンゼンスルホン酸塩は、塩化ビニル系樹脂を得る際の乳化剤であってもよく、塩化ビニル系樹脂調製時の乳化剤をそのまま、または別途添加・減量することにより添加量を調整したものであってもよい。ここで、アルキルベンゼンスルホン酸塩が０．０５重量部未満である場合、表面平滑性に劣るものとなる。一方、２．５重量部を越える場合、表面強度に劣るものとなる。 The paste vinyl chloride contains 0.05 parts by weight or more and 2.5 parts by weight or less of an alkylbenzene sulfonate, and is particularly excellent in surface smoothness and surface strength. It is preferably not more than 0.8 parts by weight and not more than 1.5 parts by weight. The alkyl benzene sulfonate may be an emulsifier used in obtaining the vinyl chloride resin, and the emulsifier used in the preparation of the vinyl chloride resin may be used as it is, or the amount added may be adjusted by adding or reducing the amount. There may be. Here, when the alkylbenzenesulfonate is less than 0.05 parts by weight, the surface smoothness is poor. On the other hand, if it exceeds 2.5 parts by weight, the surface strength will be inferior.
該ペースト塩ビは、本発明の目的・効果を逸脱しない範囲において、その他、重合開始剤、乳化剤、乳化助剤、緩衝剤、高級アルコール、高級脂肪酸、高級脂肪酸エステル、塩素化パラフィン等の分散助剤、重合度調整剤等の塩化ビニル系樹脂調製時において、一般的に添加される物質等を含むものであってもよい。 The paste polyvinyl chloride may also contain other dispersing agents such as polymerization initiators, emulsifiers, emulsifying aids, buffers, higher alcohols, higher fatty acids, higher fatty acid esters, and chlorinated paraffin, within the scope of the objects and effects of the present invention. , polymerization degree modifiers, etc., which are commonly added during the preparation of vinyl chloride resins.
該ペースト塩ビの製造方法としては、如何なる製造方法によるものであってもよく、例えば塩化ビニル系樹脂、アクリル系樹脂及びアルキルベンゼンスルホン酸塩を混合する方法、上記した塩化ビニル系樹脂ラテックスにアクリル系樹脂を混合し乾燥を行う方法、より効率的な方法としてアクリル系樹脂として水性アクリル樹脂エマルションを混合し乾燥を行う方法を挙げることができる。この際の水性アクリル樹脂エマルションとしては、市販品であってもよく、例えば（商品名）ポリトロンＥ４１８（旭化成（株）製）、（商品名）ＬＸ８７４（日本ゼオン（株）製）、（商品名）ポリトロンＡ６５５（旭化成（株）製）、（商品名）ポリトロンＺ３３２（旭化成（株）製）、（商品名）ポリトロンＥ５３００（旭化成（株）製）、（商品名）ポリトロンＡ６５５（旭化成（株）製）、（商品名）ＬＸ８５１Ｃ（日本ゼオン（株）製）、（商品名）ＬＸ８５１Ｆ２（日本ゼオン（株）製）、（商品名）ＬＸ８１４（日本ゼオン（株）製）、（商品名）ＬＸ８５５Ｅ１（日本ゼオン（株）製）、（商品名）アロンＡ－７０５５（東亜合成（株）製）、（商品名）アロンＢ－３００Ｋ（東亜合成（株）製）、（商品名）アロンＢ－５００（東亜合成（株）製）、（商品名）プライマルＴＴ－６１５（ローム・アンド・ハース社製）、（商品名）プライマルＴＴ－９３５（ローム・アンド・ハース社製）、（商品名）プライマルＡＳＥ－６０（ローム・アンド・ハース社製）、（商品名）プライマルＡＳＥ－７５（ローム・アンド・ハース社製）、（商品名）プライマルＡＳＥ－９５（ローム・アンド・ハース社製）、（商品名）プライマルＲＭ－５（ローム・アンド・ハース社製）、（商品名）ＳＮシックナーＡ－８１８（サンノプコ（株）製）、（商品名）ＳＮシックナーＡ－８５０（サンノプコ（株）製）、（商品名）オステッカーＶ－５００（日華化学（株）製）、（商品名）レオジック２５０Ｈ（日本純薬（株）製）、（商品名）レオジック８３５Ｈ（日本純薬（株）製）等を挙げることができる。中でも特に発泡性に優れるものとなることから（商品名）アロンＡ－７０５５（東亜合成（株）製）、（商品名）アロンＢ－３００Ｋ（東亜合成（株）製）、（商品名）アロンＢ－５００（東亜合成（株）製）、（商品名）プライマルＴＴ－６１５（ローム・アンド・ハース社製）、（商品名）プライマルＴＴ－９３５（ローム・アンド・ハース社製）、（商品名）プライマルＡＳＥ－６０（ローム・アンド・ハース社製）、（商品名）プライマルＡＳＥ－７５（ローム・アンド・ハース社製）、（商品名）プライマルＡＳＥ－９５（ローム・アンド・ハース社製）、（商品名）プライマルＲＭ－５（ローム・アンド・ハース社製）、（商品名）ＳＮシックナーＡ－８１８（サンノプコ（株）製）、（商品名）ＳＮシックナーＡ－８５０（サンノプコ（株）製）、（商品名）オステッカーＶ－５００（日華化学（株）製）、（商品名）レオジック２５０Ｈ（日本純薬（株）製）、（商品名）レオジック８３５Ｈ（日本純薬（株）製）等の増粘型水性アクリル樹脂エマルション、さらにアルカリ増粘型水性アクリル樹脂エマルション、重量平均分子量が５００００～２０００００のアクリル樹脂を含むｐＨ２～４のアルカリ増粘型水性アクリル樹脂エマルションであることが好ましい。また、ラテックスの乾燥方法としては、上記した塩化ビニル系樹脂ラテックスから水分を除去する方法と同様の方法を挙げることができ、中でも、効率よく水分を除去できるために、噴霧乾燥による方法が好ましい。そして、噴霧乾燥によりペースト塩ビは、取り扱い性に優れる粒状物として製造することができる。 The vinyl chloride paste may be produced by any production method, for example, a method of mixing a vinyl chloride resin, an acrylic resin and an alkylbenzene sulfonate, or a method of mixing the vinyl chloride resin latex with an acrylic resin. and drying, and as a more efficient method, a method of mixing a water-based acrylic resin emulsion as the acrylic resin and drying. The water-based acrylic resin emulsion in this case may be a commercially available product, such as (trade name) Polytron E418 (manufactured by Asahi Kasei Corporation), (trade name) LX874 (manufactured by Nippon Zeon Co., Ltd.), (trade name ) Polytron A655 (manufactured by Asahi Kasei Corp.), (trade name) Polytron Z332 (manufactured by Asahi Kasei Corp.), (trade name) Polytron E5300 (manufactured by Asahi Kasei Corp.), (trade name) Polytron A655 (manufactured by Asahi Kasei Corp.) ), (trade name) LX851C (manufactured by Nippon Zeon Co., Ltd.), (trade name) LX851F2 (manufactured by Nippon Zeon Co., Ltd.), (trade name) LX814 (manufactured by Nippon Zeon Co., Ltd.), (trade name) LX855E1 (manufactured by Nippon Zeon Co., Ltd.), (trade name) Aron A-7055 (manufactured by Toagosei Co., Ltd.), (trade name) Aron B-300K (manufactured by Toagosei Co., Ltd.), (trade name) Aron B- 500 (manufactured by Toagosei Co., Ltd.), (trade name) Primal TT-615 (manufactured by Rohm and Haas), (trade name) Primal TT-935 (manufactured by Rohm and Haas), (trade name) Primal ASE-60 (manufactured by Rohm and Haas), (trade name) Primal ASE-75 (manufactured by Rohm and Haas), (trade name) Primal ASE-95 (manufactured by Rohm and Haas), (trade name) Primal RM-5 (manufactured by Rohm and Haas), (trade name) SN Thickener A-818 (manufactured by San Nopco Co., Ltd.), (trade name) SN Thickener A-850 (manufactured by San Nopco Co., Ltd.) ), (trade name) Osticker V-500 (manufactured by Nicca Chemical Co., Ltd.), (trade name) Rheologic 250H (manufactured by Nippon Junyaku Co., Ltd.), (trade name) Rheologic 835H (manufactured by Nippon Junyaku Co., Ltd.) made) and the like. Among them, it has particularly excellent foamability (trade name) Aron A-7055 (manufactured by Toagosei Co., Ltd.), (trade name) Aron B-300K (manufactured by Toagosei Co., Ltd.), (trade name) Aron B-500 (manufactured by Toagosei Co., Ltd.), (trade name) Primal TT-615 (manufactured by Rohm and Haas), (trade name) Primal TT-935 (manufactured by Rohm and Haas), (trade name) Name) Primal ASE-60 (manufactured by Rohm and Haas), (trade name) Primal ASE-75 (manufactured by Rohm and Haas), (trade name) Primal ASE-95 (manufactured by Rohm and Haas) ), (trade name) Primal RM-5 (manufactured by Rohm and Haas), (trade name) SN Thickener A-818 (manufactured by San Nopco Co., Ltd.), (trade name) SN Thickener A-850 (manufactured by San Nopco Co., Ltd. ), (trade name) Osticker V-500 (manufactured by Nicca Chemical Co., Ltd.), (trade name) Rheologic 250H (manufactured by Nippon Junyaku Co., Ltd.), (trade name) Rheologic 835H (manufactured by Nippon Junyaku ( Co., Ltd.), an alkali-thickened aqueous acrylic resin emulsion, and an alkali-thickened aqueous acrylic resin emulsion having a pH of 2 to 4 containing an acrylic resin having a weight average molecular weight of 50,000 to 200,000. is preferred. As a method for drying the latex, the same method as the method for removing water from the vinyl chloride resin latex can be mentioned. Among them, the method by spray drying is preferable because the water can be removed efficiently. Then, by spray drying, paste PVC can be produced as a granular product that is excellent in handleability.
該ペースト塩ビは、アルキルベンゼンスルホン酸塩とアクリル系樹脂、場合によっては粒子状アクリル系樹脂とを含むペースト塩ビであり、その形状としては如何なるものであってもよく、例えばアルキルベンゼンスルホン酸塩と粒子状アクリル系樹脂とを含むペースト塩ビ粒子を挙げることができる。 The paste vinyl chloride is a paste vinyl chloride containing an alkylbenzene sulfonate and an acrylic resin, and in some cases, a particulate acrylic resin. paste vinyl chloride particles containing an acrylic resin can be mentioned.
本発明のペースト塩ビ組成物は、極めて表面強度が高く、発泡性の良好なものとなることから該ペースト塩ビ１００重量部に対して、可塑剤２０重量部以上７０重量部以下、充填剤５０重量部以下、顔料１０重量部以上３０重量部以下、安定剤１重量部以上４．５重量部以下、発泡剤１重量部以上４．５重量部以下、減粘剤１重量部以上３０重量部以下を含むものである。 The paste vinyl chloride composition of the present invention has extremely high surface strength and good foaming properties. 10 to 30 parts by weight of pigment, 1 to 4.5 parts by weight of stabilizer, 1 to 4.5 parts by weight of blowing agent, 1 to 30 parts by weight of viscosity reducing agent includes.
該可塑剤としては、例えばフタル酸ビス（２－エチルヘキシル）（ＤＯＰと略記する場合もある）、フタル酸ジイソノニル、フタル酸ジイソデシル、フタル酸ジブチル等のフタル酸エステル類；アジピン酸（２－エチルヘキシル）、アジピン酸ジイソノニル等のアジピン酸エステル類；トリメリット酸トリ（２－エチルヘキシル）、トリメリット酸トリイソデシル、トリメリット酸トリノルマルオクチル等のトリメリット酸エステル類；リン酸トリ（２－エチルヘキシル）、リン酸トリクレジル、リン酸トリキシレニル等のリン酸エステル類；ジエチレングリコールジベンゾアート、ジプロピレングリコールジベンゾアート等の安息香酸エステル；その他ポリエステル系可塑剤やセバシン酸エステル、マゼライン酸エステル、マレイン酸エステル、エポキシ化植物油等、一般に可塑剤として使用されているものを用いることができる。その際の可塑剤量はペースト塩ビ１００重量部に対して２０重量部以上７０重量部以下である。ここで、可塑剤が２０重量部未満のものである場合、高粘度となりゾルのハンドリング性が悪化する。一方、７０重量部を越える場合、発泡倍率が低下する。 Examples of the plasticizer include bis(2-ethylhexyl) phthalate (sometimes abbreviated as DOP), phthalates such as diisononyl phthalate, diisodecyl phthalate, and dibutyl phthalate; adipic acid (2-ethylhexyl); , Adipic acid esters such as diisononyl adipate; Phosphate esters such as tricresyl acid and trixylenyl phosphate; benzoate esters such as diethylene glycol dibenzoate and dipropylene glycol dibenzoate; other polyester plasticizers, sebacate esters, mazelate esters, maleate esters, epoxidized vegetable oils, etc. , those commonly used as plasticizers can be used. At that time, the amount of the plasticizer is 20 parts by weight or more and 70 parts by weight or less with respect to 100 parts by weight of the vinyl chloride paste. Here, if the plasticizer is less than 20 parts by weight, the viscosity becomes high and the handleability of the sol deteriorates. On the other hand, if it exceeds 70 parts by weight, the foaming ratio will decrease.
充填剤としては、例えば炭酸カルシウム、珪藻土、炭酸マグネシウム等が挙げられる。その際の充填剤量はペースト塩ビ１００重量部に対して５０重量部以下であり、好ましくは１５重量部以上５０重量部以下である。ここで、充填剤が５０重量部を越える場合、表面平滑性が悪化する。 Examples of fillers include calcium carbonate, diatomaceous earth, magnesium carbonate and the like. At that time, the amount of the filler is 50 parts by weight or less, preferably 15 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the vinyl chloride paste. Here, when the filler exceeds 50 parts by weight, the surface smoothness deteriorates.
顔料としては、特に限定されず、例えば酸化チタン、亜鉛華（亜鉛白）、リトポン、鉛白等が挙げられる。これらは、一種を単独で使用してもよく、二種以上を組み合わせて用いてもよい。その際の顔料量はペースト塩ビ１００重量部に対して１０重量部以上３０重量部以下であり、好ましくは１５重量部以上２５重量部以下である。ここで、顔料が１０重量部未満の場合、隠ぺい性が低下する。３０重量部をこえる場合、高粘度となりゾルのハンドリング性が悪化する。 The pigment is not particularly limited, and examples thereof include titanium oxide, zinc white (white zinc), lithopone, and white lead. These may be used individually by 1 type, and may be used in combination of 2 or more types. At that time, the amount of the pigment is 10 parts by weight or more and 30 parts by weight or less, preferably 15 parts by weight or more and 25 parts by weight or less based on 100 parts by weight of the vinyl chloride paste. Here, if the pigment is less than 10 parts by weight, the opacity is lowered. If the amount exceeds 30 parts by weight, the viscosity becomes high and the handling property of the sol deteriorates.
発泡剤としては、例えば重炭酸ナトリウム、炭酸アンモニウム、重炭酸アンモニウム、亜硝酸アンモニウム、アミド化合物、ホウ水素化ナトリウム等の無機系発泡剤；イソシアネート化合物；アゾジカルボンアミド、アゾビスイソブチロニトリル、バリウムアゾジカルボキシレート等のアゾ化合物；ｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジド、ｐ－トルエンスルホニルヒドラジド等のヒドラジン誘導体；セミカルバジド化合物；アジ化合物；ジニトロソペンタメチレンテトラミン等のニトロソ化合物；トリアゾール化合物等の有機系発泡剤が挙げられ、該発泡剤は、市販品であってもよく、例えばアゾジカルボンアミドとして、（商品名）ＡＺウルトラ１０５０（大塚化学（株）製）を挙げることができる。そして、必要に応じて上記発泡剤と亜鉛華（酸化亜鉛）等の分解促進剤を併用することも可能である。その際の発泡剤量はペースト塩ビ１００重量部に対して１重量部以上４．５重量部以下である。ここで、発泡剤が１重量部未満のものである場合、発泡倍率は低下する。一方、４．５重量部を越える場合、表面平滑性が悪化する。 Examples of foaming agents include inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, amide compounds, and sodium borohydride; isocyanate compounds; azodicarbonamide, azobisisobutyronitrile, barium azo azo compounds such as dicarboxylate; hydrazine derivatives such as p,p'-oxybisbenzenesulfonyl hydrazide and p-toluenesulfonyl hydrazide; semicarbazide compounds; azide compounds; nitroso compounds such as dinitrosopentamethylenetetramine; The foaming agent may be a commercial product, for example, (trade name) AZ Ultra 1050 (manufactured by Otsuka Chemical Co., Ltd.) can be mentioned as azodicarbonamide. If necessary, the foaming agent and a decomposition accelerator such as zinc white (zinc oxide) can be used together. The amount of the foaming agent at that time is 1 part by weight or more and 4.5 parts by weight or less with respect to 100 parts by weight of the vinyl chloride paste. Here, if the foaming agent is less than 1 part by weight, the foaming ratio is lowered. On the other hand, if it exceeds 4.5 parts by weight, the surface smoothness is deteriorated.
また、安定剤としては、例えば、エポキシ系安定剤、バリウム系安定剤、カルシウム系安定剤、スズ系安定剤、亜鉛系安定剤等が挙げられる。また、市販のカルシウム－亜鉛系、バリウム－亜鉛系等の複合安定剤を使用することもできる。そして、特に発泡性が向上することからカルシウム－亜鉛系の安定剤、例えば（商品名）ＬＦＸ８８（大協化成工業（株）製）が好ましい。その際の安定剤量はペースト塩ビ１００重量部に対して１重量部以上４．５重量部以下である。ここで、安定剤が１重量部未満のものである場合、発泡倍率、熱安定性が低下する。一方、４．５重量部を越える場合、発泡倍率が低下する。 Examples of stabilizers include epoxy-based stabilizers, barium-based stabilizers, calcium-based stabilizers, tin-based stabilizers, zinc-based stabilizers, and the like. Composite stabilizers such as commercially available calcium-zinc-based and barium-zinc-based stabilizers can also be used. Calcium-zinc-based stabilizers such as (trade name) LFX88 (manufactured by Daikyo Kasei Kogyo Co., Ltd.) are particularly preferred because they improve foamability. The amount of the stabilizer in that case is 1 part by weight or more and 4.5 parts by weight or less with respect to 100 parts by weight of the vinyl chloride paste. Here, if the amount of the stabilizer is less than 1 part by weight, the expansion ratio and thermal stability are lowered. On the other hand, if it exceeds 4.5 parts by weight, the foaming ratio will decrease.
減粘剤は、脂肪族炭化水素、芳香族炭化水素などを配合することにより、プラスチゾルの粘度を低減して加工性を向上するものであり、市販品としては例えば（商品名）Ｎ１０（ＪＸ日鉱日石（株）製）、（商品名）ＥＸＸＳＯＬＴＭＤ４０（安藤パラケミー（株）製）等を挙げることができる。その際の減粘剤量はペースト塩ビ１００重量部に対して１重量部以上３０重量部以下である。ここで、減粘剤が１重量部未満のものである場合、高粘度となりゾルのハンドリング性が悪化となる。一方、３０重量部を越える場合、表面平滑性が悪化する。 Viscosity reducing agents are used to reduce the viscosity of plastisol and improve workability by blending with aliphatic hydrocarbons, aromatic hydrocarbons, etc. Commercially available products include, for example, (trade name) N10 (JX Nikko (manufactured by Nisseki Co., Ltd.), (trade name) EXXSOL ™ D40 (manufactured by Ando Parachemie Co., Ltd.), and the like. The amount of the viscosity reducing agent at that time is 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the vinyl chloride paste. Here, when the viscosity reducing agent is less than 1 part by weight, the viscosity becomes high and the handleability of the sol deteriorates. On the other hand, if it exceeds 30 parts by weight, the surface smoothness is deteriorated.
さらに、ペースト塩ビ組成物とする際には、本発明の目的を超えない範囲でペースト塩ビ組成物に通常添加される添加剤、例えば、酸化防止剤、難燃剤、滑剤、紫外線吸収剤、顔料等の着色剤、界面活性剤、帯電防止剤等を添加してもよく、またそれらの配合量も一般に使用される範囲で差し支えない。 Furthermore, when making a paste vinyl chloride composition, additives that are usually added to the paste vinyl chloride composition within a range that does not exceed the purpose of the present invention, such as antioxidants, flame retardants, lubricants, ultraviolet absorbers, pigments, etc. Colorants, surfactants, antistatic agents, and the like may be added, and their blending amounts may be within the range generally used.
本発明のペースト塩ビ組成物は、可塑剤、充填剤、顔料、発泡剤、希釈剤、安定剤を配合することにより、成形加工性に優れるペースト塩ビゾルとすることが可能となる。そして、フィルム、シート、壁紙、床材、発泡シート等の各種用途に適用可能であり、特に表面平滑性、表面強度、発泡性等の要求される発泡体、更にはクッションフロア、発泡壁紙用として特に適したものとなる。 By blending a plasticizer, a filler, a pigment, a foaming agent, a diluent and a stabilizer, the paste vinyl chloride composition of the present invention can be made into a paste vinyl chloride sol having excellent moldability. And it can be applied to various uses such as films, sheets, wallpaper, flooring materials, foam sheets, etc. In particular, it is used for foams that require surface smoothness, surface strength, foamability, etc., as well as for cushion floors and foamed wallpapers. be particularly suitable.
本発明のペースト塩ビ組成物は、表面強度、表面平滑性、発泡性に優れる発泡体を提供することが可能であり、その工業的価値は非常に高いものである。 The paste vinyl chloride composition of the present invention can provide a foam having excellent surface strength, surface smoothness, and foamability, and has a very high industrial value.
以下に、実施例より得られたペースト塩化ビニル系樹脂組成物の評価方法を示す。 Methods for evaluating paste vinyl chloride resin compositions obtained in Examples are shown below.
＜塩化ビニル系樹脂の重合度＞
ＪＩＳ Ｋ６７２１のウベローデ粘度計を用いて、溶液粘度測定法により重合度を算出した。
<Polymerization degree of vinyl chloride resin>
The degree of polymerization was calculated by the solution viscosity measuring method using an Ubbelohde viscometer of JIS K6721.
＜発泡倍率＞
得られたペースト塩化ビニル系樹脂組成物ゾルを発泡体として以下の（１）式により算出した。
発泡倍率＝（発泡体の厚み－原反の厚み）／原反の厚み （１）
＜表面平滑性＞
得られたペースト塩化ビニル系樹脂組成物発泡体とし、その表面平滑性を目視で観察評価した。
表面平滑性の評価基準を以下に示す。
○：表面が平滑。
×：表面が粗い。
<Expansion ratio>
The obtained paste vinyl chloride resin composition sol was used as a foam and calculated by the following formula (1).
Foaming ratio = (thickness of foam - thickness of original fabric) / thickness of original fabric (1)
<Surface smoothness>
The resulting paste vinyl chloride resin composition was used as a foam, and its surface smoothness was visually observed and evaluated.
Evaluation criteria for surface smoothness are shown below.
○: The surface is smooth.
x: The surface is rough.
＜表面強度＞
壁紙工業会制定の規格「表面強化壁紙性能規定」に準拠した試験により、引っ掻き時の表面の破損状態を目視判定した。評価基準を以下に示す。
○：表面層の破れが見えるが紙等の裏打材が見えない。
×：表面が破けて紙等の裏打材が明らかに見える。
<Surface strength>
The damage state of the surface during scratching was visually determined by a test conforming to the standard "Surface Reinforced Wallpaper Performance Standards" established by the Wallpaper Industry Association. Evaluation criteria are shown below.
◯: Breakage of the surface layer is visible, but the backing material such as paper is not visible.
x: The surface is torn and the backing material such as paper is clearly visible.
＜ゾル粘度＞
ペースト塩化ビニル系樹脂組成物ゾル１５０ｍＬを、１５０ｍＬのポリプロピレン製カップに入れ、Ｂ８Ｈ型粘度計（東京計器社製）ローターＮｏ．５を用いて、回転数２０ｒｐｍの条件で粘度を評価した。ゾル粘度値が低いほどゾル粘度特性が優れることを示す。
<Sol viscosity>
150 mL of the paste vinyl chloride resin composition sol was placed in a 150 mL polypropylene cup, and a B8H type viscometer (manufactured by Tokyo Keiki Co., Ltd.) rotor No. 5 was used to evaluate the viscosity under the condition of a rotation speed of 20 rpm. A lower sol viscosity value indicates better sol viscosity characteristics.
＜隠ぺい性＞
ＪＩＳ Ａ ６９２１に準じる隠ぺい性グレースケールを用いて評価し、４級以上を合格とした。
判定基準
１級：明瞭に顕出する。
２級：顕出する。
３級：ごく僅かに顕出する。
４級：顕出しない。
<Concealability>
Evaluation was made using the opacity gray scale according to JIS A 6921, and Grade 4 or higher was considered to be acceptable.
Judgment Criteria Grade 1: Clearly manifested.
Grade 2: Reveal.
Grade 3: Very slightly revealed.
Grade 4: Not revealed.
合成例１
１ｍ３ステンレス製オートクレーブに脱イオン水３６０ｋｇ、塩化ビニルモノマー３００ｋｇ、過酸化ラウロイル５．７ｋｇ及び１５重量％ドデシルベンゼンスルホン酸ナトリウム塩水溶液３０ｋｇを仕込み、ホモジナイザーを用いて３時間循環し均質化処理を行なった後、反応系の温度を４５℃に上げて重合を開始した。重合系の圧力が低下した後、未反応塩化ビニルモノマーを回収し、固形分含有率３５重量％、平均粒子径０．５５μｍ、塩化ビニル系樹脂に対して２重量％の過酸化ラウロイルを含有する塩化ビニル系樹脂シードラテックス（ａ）を得た。
Synthesis example 1
A 1 m 3 stainless steel autoclave was charged with 360 kg of deionized water, 300 kg of vinyl chloride monomer, 5.7 kg of lauroyl peroxide, and 30 kg of a 15% by weight sodium dodecylbenzenesulfonate aqueous solution, and homogenized by circulating for 3 hours using a homogenizer. After that, the temperature of the reaction system was raised to 45° C. to initiate polymerization. After the pressure of the polymerization system is lowered, the unreacted vinyl chloride monomer is recovered, and the solid content is 35% by weight, the average particle size is 0.55 μm, and lauroyl peroxide is contained in an amount of 2% by weight based on the vinyl chloride resin. A vinyl chloride resin seed latex (a) was obtained.
合成例２
１ｍ３ステンレス製オートクレーブに脱イオン水４００ｋｇ、塩化ビニルモノマー３５０ｋｇ、１６重量％ラウリン酸カリウム水溶液２ｋｇ及び１６重量％ドデシルベンゼンスルホン酸ナトリウム塩水溶液５ｋｇを仕込み、反応系の温度を６０℃に上げて重合を開始した。重合系の圧力が低下した後、未反応塩化ビニルモノマーを回収し、固形分含有率４０重量％、平均粒子径０．１５μｍである塩化ビニル系樹脂シードラテックス（ｂ）を得た。
Synthesis example 2
400 kg of deionized water, 350 kg of vinyl chloride monomer, 2 kg of 16% by weight potassium laurate aqueous solution and 5 kg of 16% by weight sodium dodecylbenzenesulfonate aqueous solution were charged in a 1 m 3 stainless steel autoclave, and the temperature of the reaction system was raised to 60° C. for polymerization. started. After the pressure of the polymerization system was lowered, the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride resin seed latex (b) having a solid content of 40% by weight and an average particle size of 0.15 μm.
製造例１
２．５Ｌステンレス製オートクレーブに脱イオン水６１０ｇ、塩化ビニルモノマー７３０ｇ、５重量％ドデシルベンゼンスルホン酸ナトリウム塩水溶液１５ｇ、塩化ビニルモノマー１００重量部に対し合成例１により得られた平均粒子径０．５５μｍの塩化ビニル系樹脂シードラテックス（ａ）を４重量部、合成例２により得られた平均粒子径０．１５μｍの塩化ビニル系樹脂シードラテックス（ｂ）を７重量部仕込み、この反応混合物の温度を４５℃に上げて重合を開始した。重合を開始してから重合を終了までの間、塩化ビニルモノマーに対し０．７重量部の５重量％ドデシルベンゼンスルホン酸ナトリウム塩水溶液を連続的に添加した。重合圧が４５℃における塩化ビニルモノマーの飽和蒸気圧から０．２８ＭＰａまで降下したときに重合を停止し、未反応塩化ビニルモノマーを回収し、平均粒子径１．４μｍの塩化ビニル系樹脂ラテックスを得た。その際の塩化ビニル系樹脂の重合度は１６５０であった。
Production example 1
610 g of deionized water, 730 g of vinyl chloride monomer, 15 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution, 0.55 μm average particle size obtained in Synthesis Example 1 per 100 parts by weight of vinyl chloride monomer were placed in a 2.5 L stainless steel autoclave. 4 parts by weight of the vinyl chloride resin seed latex (a) and 7 parts by weight of the vinyl chloride resin seed latex (b) having an average particle size of 0.15 μm obtained in Synthesis Example 2, and the temperature of the reaction mixture was adjusted to Polymerization was initiated by raising the temperature to 45°C. From the start of the polymerization to the end of the polymerization, 0.7 parts by weight of a 5% by weight sodium dodecylbenzenesulfonate aqueous solution was continuously added to the vinyl chloride monomer. When the polymerization pressure drops from the saturated vapor pressure of the vinyl chloride monomer at 45° C. to 0.28 MPa, the polymerization is stopped, the unreacted vinyl chloride monomer is recovered, and a vinyl chloride resin latex having an average particle size of 1.4 μm is obtained. rice field. The degree of polymerization of the vinyl chloride resin at that time was 1,650.
得られた塩化ビニル系樹脂ラテックス（平均粒子径：１．４μｍ、重合度：１６５０）１ｋｇに、増粘型水性アクリル樹脂エマルション（東亜合成（株）製、（商品名）アロンＢ－３００Ｋ、平均粒子径０．１５μｍ）を４ｇ（塩化ビニル系樹脂１００重量部に対して１重量部相当）添加してから攪拌し、回転円盤式のスプレードライヤーを用い、熱風温度１６０℃、出口温度５５℃で噴霧乾燥し、ペースト塩化ビニル系樹脂を得た。 To 1 kg of the obtained vinyl chloride resin latex (average particle size: 1.4 μm, degree of polymerization: 1650), a thickened aqueous acrylic resin emulsion (manufactured by Toagosei Co., Ltd., (trade name) Aron B-300K, average 4 g (equivalent to 1 part by weight with respect to 100 parts by weight of vinyl chloride resin) of 0.15 μm particle diameter) was added, and the mixture was stirred, using a rotating disk type spray dryer, with a hot air temperature of 160 ° C. and an outlet temperature of 55 ° C. It was spray-dried to obtain a paste vinyl chloride resin.
得られたペースト塩化ビニル系樹脂は、塩化ビニル系樹脂１００重量部に対し平均粒子径１５０ｎｍのアクリル樹脂１重量部、ドデシルベンゼンスルホン酸ナトリウム塩０．９重量部を含むものであった。 The resulting paste vinyl chloride resin contained 1 part by weight of acrylic resin having an average particle diameter of 150 nm and 0.9 parts by weight of sodium dodecylbenzenesulfonate based on 100 parts by weight of vinyl chloride resin.
製造例２
２．５Ｌステンレス製オートクレーブに脱イオン水６１０ｇ、塩化ビニルモノマー７３０ｇ、５重量％ドデシルベンゼンスルホン酸ナトリウム塩水溶液１５ｇ、塩化ビニルモノマー１００重量部に対し合成例１により得られた平均粒子径０．５５μｍの塩化ビニル系樹脂シードラテックス（ａ）を４重量部、合成例２により得られた平均粒子径０．１５μｍの塩化ビニル系樹脂シードラテックス（ｂ）を７重量部仕込み、この反応混合物の温度を４５℃に上げて重合を開始した。重合を開始してから重合を終了までの間、塩化ビニルモノマーに対し０．７重量部の５重量％ドデシルベンゼンスルホン酸ナトリウム塩水溶液を連続的に添加した。重合圧が５１℃における塩化ビニルモノマーの飽和蒸気圧から０．４０ＭＰａまで降下したときに重合を停止し、未反応塩化ビニルモノマーを回収し、平均粒子径１．４μｍの塩化ビニル系樹脂ラテックスを得た。その際の塩化ビニル系樹脂の重合度は１３００であった。
Production example 2
610 g of deionized water, 730 g of vinyl chloride monomer, 15 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution, 0.55 μm average particle size obtained in Synthesis Example 1 per 100 parts by weight of vinyl chloride monomer were placed in a 2.5 L stainless steel autoclave. 4 parts by weight of the vinyl chloride resin seed latex (a) and 7 parts by weight of the vinyl chloride resin seed latex (b) having an average particle size of 0.15 μm obtained in Synthesis Example 2, and the temperature of the reaction mixture was adjusted to Polymerization was initiated by raising the temperature to 45°C. From the start of the polymerization to the end of the polymerization, 0.7 parts by weight of a 5% by weight sodium dodecylbenzenesulfonate aqueous solution was continuously added to the vinyl chloride monomer. When the polymerization pressure drops from the saturated vapor pressure of the vinyl chloride monomer at 51° C. to 0.40 MPa, the polymerization is stopped, the unreacted vinyl chloride monomer is recovered, and a vinyl chloride resin latex having an average particle size of 1.4 μm is obtained. rice field. The degree of polymerization of the vinyl chloride resin at that time was 1,300.
得られた塩化ビニル系樹脂ラテックス（平均粒子径：１．４μｍ、重合度：１３００）１ｋｇに、増粘型水性アクリル樹脂エマルション（東亜合成（株）製、（商品名）アロンＢ－３００Ｋ、平均粒子径０．１５μｍ）を４ｇ（塩化ビニル系樹脂１００重量部に対して１重量部相当）添加してから攪拌し、回転円盤式のスプレードライヤーを用い、熱風温度１６０℃、出口温度５５℃で噴霧乾燥し、ペースト塩化ビニル系樹脂を得た。 To 1 kg of the resulting vinyl chloride resin latex (average particle size: 1.4 μm, degree of polymerization: 1300), a thickened aqueous acrylic resin emulsion (manufactured by Toagosei Co., Ltd., (trade name) Aron B-300K, average 4 g (equivalent to 1 part by weight with respect to 100 parts by weight of vinyl chloride resin) of 0.15 μm particle diameter) was added, and the mixture was stirred, using a rotating disk type spray dryer, with a hot air temperature of 160 ° C. and an outlet temperature of 55 ° C. It was spray-dried to obtain a paste vinyl chloride resin.
得られたペースト塩化ビニル系樹脂は、塩化ビニル系樹脂１００重量部に対し平均粒子径１５０ｎｍのアクリル樹脂１重量部、ドデシルベンゼンスルホン酸ナトリウム塩０．９重量部を含むものであった。 The resulting paste vinyl chloride resin contained 1 part by weight of acrylic resin having an average particle diameter of 150 nm and 0.9 parts by weight of sodium dodecylbenzenesulfonate based on 100 parts by weight of vinyl chloride resin.
製造例３
２．５Ｌステンレス製オートクレーブに脱イオン水６１０ｇ、塩化ビニルモノマー７３０ｇ、５重量％ドデシルベンゼンスルホン酸ナトリウム塩水溶液１５ｇ、塩化ビニルモノマー１００重量部に対し合成例１により得られた平均粒子径０．５５μｍの塩化ビニル系樹脂シードラテックス（ａ）を４重量部、合成例２により得られた平均粒子径０．１５μｍの塩化ビニル系樹脂シードラテックス（ｂ）を７重量部仕込み、この反応混合物の温度を４５℃に上げて重合を開始した。重合を開始してから重合を終了までの間、塩化ビニルモノマーに対し０．７重量部の５重量％ドデシルベンゼンスルホン酸ナトリウム塩水溶液を連続的に添加した。重合圧が４５℃における塩化ビニルモノマーの飽和蒸気圧から０．２８ＭＰａまで降下したときに重合を停止し、未反応塩化ビニルモノマーを回収し、平均粒子径１．４μｍの塩化ビニル系樹脂ラテックスを得た。その際の塩化ビニル系樹脂の重合度は１６５０であった。
Production example 3
610 g of deionized water, 730 g of vinyl chloride monomer, 15 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution, 0.55 μm average particle size obtained in Synthesis Example 1 per 100 parts by weight of vinyl chloride monomer were placed in a 2.5 L stainless steel autoclave. 4 parts by weight of the vinyl chloride resin seed latex (a) and 7 parts by weight of the vinyl chloride resin seed latex (b) having an average particle size of 0.15 μm obtained in Synthesis Example 2, and the temperature of the reaction mixture was adjusted to Polymerization was initiated by raising the temperature to 45°C. From the start of the polymerization to the end of the polymerization, 0.7 parts by weight of a 5% by weight sodium dodecylbenzenesulfonate aqueous solution was continuously added to the vinyl chloride monomer. When the polymerization pressure drops from the saturated vapor pressure of the vinyl chloride monomer at 45° C. to 0.28 MPa, the polymerization is stopped, the unreacted vinyl chloride monomer is recovered, and a vinyl chloride resin latex having an average particle size of 1.4 μm is obtained. rice field. The degree of polymerization of the vinyl chloride resin at that time was 1,650.
得られた塩化ビニル系樹脂ラテックス（平均粒子径：１．４μｍ、重合度：１６５０）１ｋｇに、増粘型水性アクリル樹脂エマルション（東亜合成（株）製、（商品名）アロンＢ－３００Ｋ、平均粒子径０．１５μｍ）を６ｇ（塩化ビニル系樹脂１００重量部に対して１．５重量部相当）添加してから攪拌し、回転円盤式のスプレードライヤーを用い、熱風温度１６０℃、出口温度５５℃で噴霧乾燥し、ペースト塩化ビニル系樹脂を得た。 To 1 kg of the obtained vinyl chloride resin latex (average particle size: 1.4 μm, degree of polymerization: 1650), a thickened aqueous acrylic resin emulsion (manufactured by Toagosei Co., Ltd., (trade name) Aron B-300K, average 6 g (equivalent to 1.5 parts by weight with respect to 100 parts by weight of vinyl chloride resin) of 0.15 μm in particle diameter) was added, and the mixture was stirred, using a rotating disk type spray dryer, hot air temperature was 160° C., outlet temperature was 55° C. It was spray-dried at ℃ to obtain a paste vinyl chloride resin.
得られたペースト塩化ビニル系樹脂は、塩化ビニル系樹脂１００重量部に対し平均粒子径１５０ｎｍのアクリル樹脂１．５重量部、ドデシルベンゼンスルホン酸ナトリウム塩０．９重量部を含むものであった。 The resulting paste vinyl chloride resin contained 1.5 parts by weight of acrylic resin having an average particle diameter of 150 nm and 0.9 parts by weight of sodium dodecylbenzenesulfonate based on 100 parts by weight of vinyl chloride resin.
実施例１
製造例１により得られたペースト塩化ビニル系樹脂１００重量部に対し、可塑剤としてジイソノニルフタレート（（株）ジェイ・プラス製、グレード工業用）３０重量部、充填剤として炭酸カルシウム（三共精粉（株）製、グレード一級）２０重量部、顔料として酸化チタン（テイカ（株）製、（商品名）ＪＲ６００Ａ）１５重量部、発泡剤としてアゾジカルボンアミド（大塚化学（株）製、（商品名）ＡＺウルトラ１０５０）３重量部、脱芳香族化炭化水素類である減粘剤（安藤パラケミー（株）製、（商品名）ＥＸＸＳＯＬＴＭＤ４０）１０重量部、安定剤としてＣａ/Ｚｎ系安定剤（大協化成工業（株）製、（商品名）ＬＦＸ８８）３重量部を配合しペースト塩化ビニル系樹脂組成物とし、ディゾルバーを用いて混練し、ペースト塩化ビニル系樹脂組成物ゾルを得た。
Example 1
For 100 parts by weight of the paste vinyl chloride resin obtained in Production Example 1, 30 parts by weight of diisononyl phthalate (manufactured by J-Plus Co., Ltd., grade industrial use) as a plasticizer and calcium carbonate (Sankyo Seifun ( Co., Ltd., Grade 1) 20 parts by weight, 15 parts by weight of titanium oxide (Tayca Co., Ltd., (trade name) JR600A) as a pigment, and azodicarbonamide (Otsuka Chemical Co., Ltd., (trade name)) as a foaming agent. AZ Ultra 1050) 3 parts by weight, 10 parts by weight of a viscosity reducing agent (manufactured by Ando Parachemie Co., Ltd., (trade name) EXXSOL TM D40) which is a dearomatized hydrocarbon, and a Ca/Zn-based stabilizer ( Daikyo Kasei Kogyo Co., Ltd., (trade name) LFX88) was mixed with 3 parts by weight to form a paste vinyl chloride resin composition, which was kneaded using a dissolver to obtain a paste vinyl chloride resin composition sol.
得られたペースト塩化ビニル系樹脂組成物ビゾルの粘度は１１０００ｍＰａ・ｓであった。 The obtained paste vinyl chloride resin composition Visol had a viscosity of 11000 mPa·s.
また、得られたペースト円環ビニル系樹脂組成物ゾルを、予め１９０℃で１０秒加熱した難燃紙上に０．１２ｍｍの厚みでコーティングし、１９０℃で８秒加熱することにより、原反を得た。得られた原反の厚みを測定した後、２２５℃で２５秒加熱することにより発泡体を得た。その後、得られた発泡体の厚みを測定し、発泡倍率、表面平滑性、隠ぺい性を評価した。試験結果を表１に示す。発泡倍率は６．９倍であり、表面平滑性、表面強度に優れるものであった。 In addition, the obtained paste annular vinyl resin composition sol was coated in a thickness of 0.12 mm on a flame-retardant paper heated at 190° C. for 10 seconds in advance, and heated at 190° C. for 8 seconds to obtain a raw sheet. Obtained. After measuring the thickness of the obtained original sheet, it was heated at 225° C. for 25 seconds to obtain a foam. After that, the thickness of the obtained foam was measured, and the expansion ratio, surface smoothness and hiding property were evaluated. Table 1 shows the test results. The expansion ratio was 6.9 times, and the surface smoothness and surface strength were excellent.
実施例２
可塑剤４０重量部、減粘剤１５重量部とした以外は、実施例１と同様の方法によりペースト塩化ビニル系樹脂組成物、ペースト塩化ビニル系樹脂組成物ゾルを調製し、発泡体としての評価を行った。発泡倍率、表面平滑性、セル構造を評価した結果を表１に示す。発泡倍率は５．６倍であり、表面平滑性、表面強度に優れるものであった。
Example 2
A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1 except that the plasticizer was 40 parts by weight and the viscosity reducer was 15 parts by weight, and evaluated as a foam. did Table 1 shows the results of evaluating the expansion ratio, surface smoothness, and cell structure. The expansion ratio was 5.6 times, and the surface smoothness and surface strength were excellent.
実施例３
可塑剤４０重量部、減粘剤２０重量部とした以外は、実施例１と同様の方法によりペースト塩化ビニル系樹脂組成物、ペースト塩化ビニル系樹脂組成物ゾルを調製し、発泡体としての評価を行った。発泡倍率、表面平滑性、セル構造を評価した結果を表１に示す。発泡倍率は５．８倍であり、表面平滑性、表面強度に優れるものであった。
Example 3
A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1 except that the plasticizer was 40 parts by weight and the viscosity reducer was 20 parts by weight, and evaluated as a foam. did Table 1 shows the results of evaluating the expansion ratio, surface smoothness, and cell structure. The expansion ratio was 5.8, and the surface smoothness and surface strength were excellent.
実施例４
可塑剤５０重量部、発泡剤４重量部、安定剤４重量部とした以外は、実施例１と同様の方法によりペースト塩化ビニル系樹脂組成物、ペースト塩化ビニル系樹脂組成物ゾルを調製し、発泡体としての評価を行った。発泡倍率、表面平滑性、セル構造を評価した結果を表１に示す。発泡倍率は６．７倍であり、表面平滑性、表面強度に優れるものであった。
Example 4
A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1 except that the plasticizer was 50 parts by weight, the foaming agent was 4 parts by weight, and the stabilizer was 4 parts by weight. It was evaluated as a foam. Table 1 shows the results of evaluating the expansion ratio, surface smoothness, and cell structure. The expansion ratio was 6.7 times, and the surface smoothness and surface strength were excellent.
実施例５
可塑剤４０重量部、充填剤０重量部とした以外は、実施例１と同様の方法によりペースト塩化ビニル系樹脂組成物、ペースト塩化ビニル系樹脂組成物ゾルを調製し、発泡体としての評価を行った。発泡倍率、表面平滑性、セル構造を評価した結果を表１に示す。発泡倍率は７．１倍であり、表面平滑性、表面強度に優れるものであった。
Example 5
A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1 except that the plasticizer was 40 parts by weight and the filler was 0 parts by weight, and evaluated as a foam. gone. Table 1 shows the results of evaluating the expansion ratio, surface smoothness, and cell structure. The expansion ratio was 7.1 times, and the surface smoothness and surface strength were excellent.
実施例６
製造例２により得られたペースト塩化ビニル系樹脂１００重量部に対し、可塑剤としてジイソノニルフタレート（（株）ジェイ・プラス製、グレード工業用）４０重量部、充填剤として炭酸カルシウム（三共精粉（株）製、グレード一級）２０重量部、顔料として酸化チタン（テイカ（株）製、（商品名）ＪＲ６００Ａ）１５重量部、発泡剤としてアゾジカルボンアミド（大塚化学（株）製、（商品名）ＡＺウルトラ１０５０）３重量部、脱芳香族化炭化水素類である減粘剤（安藤パラケミー（株）製、（商品名）ＥＸＳＳＯＬＴＭＤ４０）１０重量部、安定剤としてＣａ／Ｚｎ系安定剤（大協化成工業（株）製、（商品名）ＬＦＸ８８）３重量部を配合しペースト塩化ビニル系樹脂組成物とし、ディゾルバーを用いて混練し、ペースト塩化ビニル系樹脂組成物ゾルを得た。
Example 6
For 100 parts by weight of the paste vinyl chloride resin obtained in Production Example 2, 40 parts by weight of diisononyl phthalate (manufactured by J-Plus Co., Ltd., grade industrial use) as a plasticizer and calcium carbonate as a filler (Sankyo Seifun ( Co., Ltd., Grade 1) 20 parts by weight, 15 parts by weight of titanium oxide (Tayca Co., Ltd., (trade name) JR600A) as a pigment, and azodicarbonamide (Otsuka Chemical Co., Ltd., (trade name)) as a foaming agent. AZ Ultra 1050) 3 parts by weight, 10 parts by weight of a dearomatized hydrocarbon viscosity reducing agent (manufactured by Ando Parachemie Co., Ltd., (trade name) EXSSOL TM D40), a Ca / Zn-based stabilizer as a stabilizer ( Daikyo Kasei Kogyo Co., Ltd., (trade name) LFX88) was mixed with 3 parts by weight to form a paste vinyl chloride resin composition, which was kneaded using a dissolver to obtain a paste vinyl chloride resin composition sol.
得られたペースト塩化ビニル系樹脂組成物ビゾルの粘度は３７００ｍＰａ・ｓであった。 The obtained paste vinyl chloride resin composition Visol had a viscosity of 3700 mPa·s.
また、得られたペースト円環ビニル系樹脂組成物ゾルを、予め１９０℃で１０秒加熱した難燃紙上に０．１２ｍｍの厚みでコーティングし、１９０℃で８秒加熱することにより、原反を得た。得られた原反の厚みを測定した後、２２５℃で２５秒加熱することにより発泡体を得た。その後、得られた発泡体の厚みを測定し、発泡倍率、表面平滑性、隠ぺい性を評価した。試験結果を表１に示す。発泡倍率は６．３倍であり、表面平滑性、表面強度に優れるものであった。 In addition, the obtained paste annular vinyl resin composition sol was coated in a thickness of 0.12 mm on a flame-retardant paper heated at 190° C. for 10 seconds in advance, and heated at 190° C. for 8 seconds to obtain a raw sheet. Obtained. After measuring the thickness of the obtained original sheet, it was heated at 225° C. for 25 seconds to obtain a foam. After that, the thickness of the obtained foam was measured, and the expansion ratio, surface smoothness and hiding property were evaluated. Table 1 shows the test results. The expansion ratio was 6.3 times, and the surface smoothness and surface strength were excellent.
実施例７
製造例３により得られたペースト塩化ビニル系樹脂１００重量部に対し、可塑剤としてジイソノニルフタレート（（株）ジェイ・プラス製、グレード工業用）４０重量部、充填剤として炭酸カルシウム（三共精粉（株）製、グレード一級）２０重量部、顔料として酸化チタン（テイカ（株）製、（商品名）ＪＲ６００Ａ）１５重量部、発泡剤としてアゾジカルボンアミド（大塚化学（株）製、（商品名）ＡＺウルトラ１０５０）３重量部、脱芳香族化炭化水素類である減粘剤（安藤パラケミー（株）製、（商品名）ＥＸＳＳＯＬＴＭＤ４０）１０重量部、安定剤としてＣａ／Ｚｎ系安定剤（大協化成工業（株）製、（商品名）ＬＦＸ８８）３重量部を配合しペースト塩化ビニル系樹脂組成物とし、ディゾルバーを用いて混練し、ペースト塩化ビニル系樹脂組成物ゾルを得た。
Example 7
For 100 parts by weight of the paste vinyl chloride resin obtained in Production Example 3, 40 parts by weight of diisononyl phthalate (manufactured by J-Plus Co., Ltd., grade industrial use) as a plasticizer and calcium carbonate (Sankyo Seifun ( Co., Ltd., Grade 1) 20 parts by weight, 15 parts by weight of titanium oxide (Tayca Co., Ltd., (trade name) JR600A) as a pigment, and azodicarbonamide (Otsuka Chemical Co., Ltd., (trade name)) as a foaming agent. AZ Ultra 1050) 3 parts by weight, 10 parts by weight of a dearomatized hydrocarbon viscosity reducing agent (manufactured by Ando Parachemie Co., Ltd., (trade name) EXSSOL TM D40), a Ca / Zn-based stabilizer as a stabilizer ( Daikyo Kasei Kogyo Co., Ltd., (trade name) LFX88) was mixed with 3 parts by weight to form a paste vinyl chloride resin composition, which was kneaded using a dissolver to obtain a paste vinyl chloride resin composition sol.
得られたペースト塩化ビニル系樹脂組成物ビゾルの粘度は４７５０ｍＰａ・ｓであった。 The obtained paste vinyl chloride resin composition Visol had a viscosity of 4750 mPa·s.
また、得られたペースト円環ビニル系樹脂組成物ゾルを、予め１９０℃で１０秒加熱した難燃紙上に０．１２ｍｍの厚みでコーティングし、１９０℃で８秒加熱することにより、原反を得た。得られた原反の厚みを測定した後、２２５℃で２５秒加熱することにより発泡体を得た。その後、得られた発泡体の厚みを測定し、発泡倍率、表面平滑性、隠ぺい性を評価した。試験結果を表１に示す。発泡倍率は５．６倍であり、表面平滑性、表面強度に優れるものであった。 In addition, the obtained paste annular vinyl resin composition sol was coated in a thickness of 0.12 mm on a flame-retardant paper heated at 190° C. for 10 seconds in advance, and heated at 190° C. for 8 seconds to obtain a raw sheet. Obtained. After measuring the thickness of the obtained original sheet, it was heated at 225° C. for 25 seconds to obtain a foam. After that, the thickness of the obtained foam was measured, and the expansion ratio, surface smoothness and hiding property were evaluated. Table 1 shows the test results. The expansion ratio was 5.6 times, and the surface smoothness and surface strength were excellent.
比較例１
可塑剤８０重量部とした以外は、実施例１と同様の方法によりペースト塩化ビニル系樹脂組成物、ペースト塩化ビニル系樹脂組成物ゾルを調製し、発泡体としての評価を行った。発泡倍率、表面平滑性、セル構造を評価した結果を表２に示す。発泡倍率は４．２倍であり発泡性に劣るものであった。
Comparative example 1
A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1 except that 80 parts by weight of the plasticizer was used, and evaluated as a foam. Table 2 shows the results of evaluating the expansion ratio, surface smoothness, and cell structure. The foaming ratio was 4.2 times, indicating poor foamability.
比較例２
可塑剤４０重量部、顔料０部とした以外は、実施例１と同様の方法によりペースト塩化ビニル系樹脂組成物、ペースト塩化ビニル系樹脂組成物ゾルを調製し、発泡体としての評価を行った。発泡倍率、表面平滑性、セル構造を評価した結果を表２に示した。隠ぺい性、表面平滑性に劣るものであった。
Comparative example 2
A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1 except that 40 parts by weight of the plasticizer and 0 part of the pigment were used, and evaluated as a foam. . Table 2 shows the results of evaluating the expansion ratio, surface smoothness, and cell structure. It was inferior in concealability and surface smoothness.
比較例３
可塑剤４０重量部、充填剤１００重量部とした以外は、実施例１と同様の方法によりペースト塩化ビニル系樹脂組成物、ペースト塩化ビニル系樹脂組成物ゾルを調製し、発泡体としての評価を行った。発泡倍率、表面平滑性、セル構造を評価した結果を表２に示した。粘度、表面強度、表面平滑性に劣るものであった。
Comparative example 3
A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1 except that the plasticizer was 40 parts by weight and the filler was 100 parts by weight, and evaluated as a foam. gone. Table 2 shows the results of evaluating the expansion ratio, surface smoothness, and cell structure. It was inferior in viscosity, surface strength and surface smoothness.
比較例４
可塑剤４０重量部、発泡剤７重量部とした以外は、実施例１と同様の方法によりペースト塩化ビニル系樹脂組成物、ペースト塩化ビニル系樹脂組成物ゾルを調製し、発泡体としての評価を行った。発泡倍率、表面平滑性、セル構造を評価した結果を表２に示す。発泡倍率は４．６倍であり、表面強度、表面平滑性に劣るものであった。
Comparative example 4
A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1 except that the plasticizer was 40 parts by weight and the foaming agent was 7 parts by weight, and evaluated as a foam. gone. Table 2 shows the results of evaluating the expansion ratio, surface smoothness, and cell structure. The expansion ratio was 4.6 times, and the surface strength and surface smoothness were inferior.
本発明のペースト塩化ビニル系樹脂組成物は、発泡性を備え、高い表面強度、表面平滑性を提供するものであり、特に発泡壁紙用として優れた特性を有することから、その産業的価値は極めて高いものである。 The paste vinyl chloride resin composition of the present invention is foamable, provides high surface strength and surface smoothness, and has excellent properties especially for foamed wallpaper, so its industrial value is extremely high. It is expensive.
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