JP2005187642A - Vinyl chloride-based resin composition for paste, method for producing the same and application thereof - Google Patents
Vinyl chloride-based resin composition for paste, method for producing the same and application thereof Download PDFInfo
- Publication number
- JP2005187642A JP2005187642A JP2003430827A JP2003430827A JP2005187642A JP 2005187642 A JP2005187642 A JP 2005187642A JP 2003430827 A JP2003430827 A JP 2003430827A JP 2003430827 A JP2003430827 A JP 2003430827A JP 2005187642 A JP2005187642 A JP 2005187642A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- resin composition
- paste
- chloride resin
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000011342 resin composition Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title description 13
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 31
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- -1 inorganic acid salt Chemical class 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 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 claims abstract description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 13
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 239000002952 polymeric resin Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 description 31
- 239000000047 product Substances 0.000 description 25
- 229920001944 Plastisol Polymers 0.000 description 15
- 238000000465 moulding Methods 0.000 description 15
- 239000004999 plastisol Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000004014 plasticizer Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000008187 granular material Substances 0.000 description 8
- 239000004088 foaming agent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- 238000010022 rotary screen printing Methods 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229910000004 White lead Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 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
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000001175 rotational moulding Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 1
- HDIFHQMREAYYJW-FMIVXFBMSA-N 2,3-dihydroxypropyl (e)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C\CCCCCCCC(=O)OCC(O)CO HDIFHQMREAYYJW-FMIVXFBMSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- PHDVPEOLXYBNJY-KTKRTIGZSA-N 2-(2-hydroxyethoxy)ethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCOCCO PHDVPEOLXYBNJY-KTKRTIGZSA-N 0.000 description 1
- QUYITUXSUUKIRL-ZDKIGPTLSA-N 2-(2-hydroxyethoxy)ethyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCCOCCO QUYITUXSUUKIRL-ZDKIGPTLSA-N 0.000 description 1
- WGIMXKDCVCTHGW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOCCO WGIMXKDCVCTHGW-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
- RTGQGAXEHFZMBG-UHFFFAOYSA-N 2-(2-nonanoyloxyethoxy)ethyl nonanoate Chemical compound CCCCCCCCC(=O)OCCOCCOC(=O)CCCCCCCC RTGQGAXEHFZMBG-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- NUCFNMOPTGEHQA-UHFFFAOYSA-N 3-bromo-2h-pyrazolo[4,3-c]pyridine Chemical compound C1=NC=C2C(Br)=NNC2=C1 NUCFNMOPTGEHQA-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 1
- LEUWBMAQQQENOO-UHFFFAOYSA-N 4-(4-chlorophenyl)-6-methyl-2-oxo-3,4-dihydro-1h-pyridine-5-carboxylic acid Chemical compound C1C(=O)NC(C)=C(C(O)=O)C1C1=CC=C(Cl)C=C1 LEUWBMAQQQENOO-UHFFFAOYSA-N 0.000 description 1
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-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
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- LBNALQDAKDLDRW-UHFFFAOYSA-N OC(=O)CCCCCCCCC(O)=O.CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC Chemical class OC(=O)CCCCCCCCC(O)=O.CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC LBNALQDAKDLDRW-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001278 adipic acid derivatives Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 150000001535 azelaic acid derivatives Chemical class 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- RAKMKCZMVZBODU-PIQLPZBWSA-L barium(2+);(z)-12-hydroxyoctadec-9-enoate Chemical compound [Ba+2].CCCCCCC(O)C\C=C/CCCCCCCC([O-])=O.CCCCCCC(O)C\C=C/CCCCCCCC([O-])=O RAKMKCZMVZBODU-PIQLPZBWSA-L 0.000 description 1
- ROPXFXOUUANXRR-YPKPFQOOSA-N bis(2-ethylhexyl) (z)-but-2-enedioate Chemical compound CCCCC(CC)COC(=O)\C=C/C(=O)OCC(CC)CCCC ROPXFXOUUANXRR-YPKPFQOOSA-N 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- WXZOXVVKILCOPG-UHFFFAOYSA-N bis(2-ethylhexyl) benzene-1,3-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC(C(=O)OCC(CC)CCCC)=C1 WXZOXVVKILCOPG-UHFFFAOYSA-N 0.000 description 1
- IMIOEHJVRZOQBJ-UHFFFAOYSA-N bis(6-methylheptyl) benzene-1,3-dicarboxylate Chemical compound CC(C)CCCCCOC(=O)C1=CC=CC(C(=O)OCCCCCC(C)C)=C1 IMIOEHJVRZOQBJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 150000002237 fumaric acid derivatives Chemical class 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
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- 239000012760 heat stabilizer Substances 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
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- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
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- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
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- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- MXHBQKVKHGQWRB-UHFFFAOYSA-N trihexyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC)C(C(=O)OCCCCCC)=C1 MXHBQKVKHGQWRB-UHFFFAOYSA-N 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- WDRCVXGINNJWPH-UHFFFAOYSA-N tris(6-methylheptyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC(C)C)C(C(=O)OCCCCCC(C)C)=C1 WDRCVXGINNJWPH-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ペースト用塩化ビニル系樹脂組成物、その製造方法及び用途に関するものである。 The present invention relates to a vinyl chloride resin composition for paste, a method for producing the same, and a use thereof.
ペースト用塩化ビニル系樹脂組成物は、難燃性等に優れた特性を有し、しかも作業性にも優れているので、壁材、床材、レザー、帆布、車両内装品、鋼板コート、綿材コート、糸コート、作業手袋、玩具、日用雑貨品等の製造に汎用されている。
最近、消費者の嗜好として、表面光沢がなく、外観の落着きのある艶消し製品が求められている。
このため、上記の塩化ビニル系樹脂製品についても、表面艶消しの研究がなされている。このような艶消し製品に関する従来例としては、例えば、（１）塩化ビニル系プラスチゾルを賦形した後、加熱してゲル化させ、続いてさらに高温で加熱して溶融し、冷却して成形体を製造する方法において、賦形した後から溶融するまでの間に賦形体の表面に多価アルコールを塗布することを特徴とする塩化ビニル系樹脂ペーストの成形体の製造方法（特許文献１）、（２）塩化ビニル系プラスチゾルを賦形した後、加熱してゲル化させ、続いてさらに高温で加熱して溶融し、冷却して成形体を製造する方法において、賦形した後から溶融するまでの間に賦形体の表面に多価アルコールと亜鉛含有安定剤の混合液を塗布することを特徴とする塩化ビニル系樹脂ペーストの成形体の製造方法（特許文献２）、（３）塩化ビニル系樹脂１００グラムに対して、カルボン酸亜鉛化合物０．００２〜０．０２グラムモル及び１分子中に２個以上のアルコール性水酸基を有する化合物を該カルボン酸亜鉛化合物１グラムモルに対して０．３〜３グラムモルの割合いにて配合することを特徴とする塩化ビニル系樹脂組成物（特許文献３）、（４）塩化ビニル系重合体１００重量部、可塑剤３０〜３００重量部および多価アルコール０．３〜５重量部とからなるペースト用樹脂組成物（特許文献４）、等が挙げられる。
Since the vinyl chloride resin composition for paste has excellent properties such as flame retardancy, it also has excellent workability, so it can be used for wall materials, flooring materials, leather, canvas, vehicle interior parts, steel plate coats, cotton Widely used in the manufacture of material coats, thread coats, work gloves, toys, daily goods.
Recently, there is a demand for a matte product that does not have surface gloss and has a calm appearance as a consumer preference.
For this reason, research on the matte surface of the above vinyl chloride resin products has also been made. Conventional examples of such matte products include, for example, (1) after forming a vinyl chloride plastisol, heating to gel, then heating and melting at a higher temperature, cooling, and molding In the method for producing a molded article of a vinyl chloride resin paste, characterized in that a polyhydric alcohol is applied to the surface of the shaped body after it is shaped and melted (Patent Document 1), (2) After shaping the vinyl chloride plastisol, it is heated to gel, then heated and melted at a higher temperature, and cooled to produce a molded product, from after shaping to melting A method for producing a molded article of a vinyl chloride resin paste, characterized in that a mixture of a polyhydric alcohol and a zinc-containing stabilizer is applied to the surface of the shaped article between (patent document 2) and (3) vinyl chloride 100 g of resin 0.003 to 0.02 gram mole of the zinc carboxylate compound and 0.3 to 3 gram mole of the compound having two or more alcoholic hydroxyl groups in one molecule with respect to 1 gram mole of the zinc carboxylate compound. A vinyl chloride resin composition (Patent Document 3), (4) 100 parts by weight of a vinyl chloride polymer, 30 to 300 parts by weight of a plasticizer, and 0.3 to 0.3 parts of a polyhydric alcohol. Examples thereof include a resin composition for paste composed of 5 parts by weight (Patent Document 4).
しかし、上記の従来法は、何れも満足し得るものではない。
即ち、従来法（１）と（２）については、何れも艶消し剤を被覆するものであるので、被覆、乾燥のための別工程が必要であり、経済性の点で劣るばかりでなく、ロータリースクリーン印刷によるもの等のように、被覆処理が困難な製品には適用することができないという欠点がある。
次に、従来法（３）と（４）については、前者は、艶消し成分の内、カルボン酸亜鉛化合物は油溶性、もう一方の成分のカルボン酸亜鉛化合物は水溶性であり、両成分は親和性に欠け、その結果、艶消し成分の分散がよくないので、その艶消し性は十分ではない点、また、後者は、艶消し成分の多価アルコールの艶消し特性は十分ではない点で、何れも、その艶消し効果は満足し得るものではない。
従って、汎用性のある、優れた艶消し効果を呈する、ペースト用塩化ビニル系樹脂組成物は未だなく、その開発が待たれている。
However, none of the above conventional methods are satisfactory.
That is, the conventional methods (1) and (2) are both coated with a matting agent, so that separate steps for coating and drying are required, which is not only inferior in terms of economy, There is a drawback in that it cannot be applied to products that are difficult to coat, such as by rotary screen printing.
Next, for the conventional methods (3) and (4), the former is a matte component, the zinc carboxylate compound is oil-soluble, and the other component zinc carboxylate compound is water-soluble. Lack of affinity, resulting in poor dispersion of the matting component, so that the matting property is not sufficient, and the latter is that the matting properties of the polyhydric alcohol of the matting component is not sufficient In any case, the matting effect is not satisfactory.
Therefore, a vinyl chloride resin composition for paste that exhibits an excellent matting effect with versatility has not yet been developed, and its development is awaited.
本発明の課題は、汎用性のある、優れた艶消し効果を呈する、ペースト用塩化ビニル系樹脂組成物を提供することにある。 An object of the present invention is to provide a vinyl chloride resin composition for paste that exhibits versatility and an excellent matting effect.
本発明者らは、上記の課題を解決するため鋭意研究を重ねたところ、塩化ビニル系重合体に対して、艶消し成分として、特定の２種類の化合物を特定量配合すると、優れた艶消し性を呈するペースト用塩化ビニル系樹脂組成物が得られることを知り、更に研究を重ねた結果、本発明を完成するに至った。 The inventors of the present invention have made extensive studies to solve the above-mentioned problems. As a result, when a specific amount of two specific types of compounds are blended with the vinyl chloride polymer as a matting component, excellent matting is achieved. As a result of knowing that a vinyl chloride resin composition for paste exhibiting properties can be obtained and further researching it, the present invention has been completed.
本発明は、以下の発明から構成されるものである。
１．塩化ビニル系重合体１００重量部当たり、多価アルコール０．２〜５重量部及び水溶性亜鉛化合物０．２〜５重量部からなる艶消し成分を含有することを特徴とするペースト用塩化ビニル系樹脂組成物。
２．多価アルコールが、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、ジトリメチロールプロパン、又はグリセリンから選択された１種又は２種以上の化合物である上記１記載のペースト用塩化ビニル系樹脂組成物。
３．水溶性亜鉛化合物が、亜鉛の無機酸塩である上記１又は２記載のペースト用塩化ビニル系樹脂組成物。
４．亜鉛の無機酸塩が、塩化亜鉛、硫酸亜鉛、又は硝酸亜鉛である上記１、２又は３記載のペースト用塩化ビニル系樹脂組成物。
５．塩化ビニル系重合体、多価アルコール及び水溶性亜鉛化合物からなる水性分散液を噴霧乾燥してなる粉粒体とすることを特徴とする上記１、２、３又は４記載のペースト用塩化ビニル系樹脂組成物の製造方法。
６．上記１、２、３、４又は５記載のペースト用塩化ビニル系樹脂組成物から製造された表面艶消し製品。
The present invention comprises the following inventions.
1. A vinyl chloride system for pastes comprising a matting component comprising 0.2 to 5 parts by weight of a polyhydric alcohol and 0.2 to 5 parts by weight of a water-soluble zinc compound per 100 parts by weight of a vinyl chloride polymer Resin composition.
2. 2. The vinyl chloride resin composition for paste according to 1 above, wherein the polyhydric alcohol is one or more compounds selected from trimethylolpropane, pentaerythritol, dipentaerythritol, ditrimethylolpropane, or glycerin.
3. 3. The vinyl chloride resin composition for paste according to 1 or 2 above, wherein the water-soluble zinc compound is an inorganic acid salt of zinc.
4). 4. The vinyl chloride resin composition for paste according to 1, 2 or 3, wherein the zinc inorganic acid salt is zinc chloride, zinc sulfate or zinc nitrate.
5). 5. The vinyl chloride system for paste according to the above 1, 2, 3 or 4, characterized in that it is a powder granule obtained by spray drying an aqueous dispersion comprising a vinyl chloride polymer, a polyhydric alcohol and a water-soluble zinc compound. A method for producing a resin composition.
6). A matte product produced from the vinyl chloride resin composition for paste according to the above 1, 2, 3, 4 or 5.
本発明の特徴は、塩化ビニル系重合体に対して、艶消し成分として、特定の２種類の化合物、即ち、多価アルコール及び水溶性亜鉛化合物を特定量配合することにより、汎用性のある、優れた艶消し性を呈するペースト用塩化ビニル系樹脂組成物を得た点にある。
本発明の艶消し成分である、多価アルコールと水溶性亜鉛化合物は、何れも水溶性であるため、両化合物の親和性は極めてよく、而も、塩化ビニル系樹脂の水性分散液に均質に分散するという特性を有する。
ペースト用塩化ビニル系樹脂は、通常、乳化剤を含んだ水性媒体を用いた乳化重合法やミクロ懸濁重合法により、水性分散液として得られるが、本発明の艶消し成分は水溶性であって、該分散液と親和性があるので、本艶消し成分は、製造された塩化ビニル系樹脂分散液とそのまま配合しても、均質に分散し、特段の艶消し効果を発揮するという利点がある。
従って、本発明のペースト用塩化ビニル系樹脂組成物は、上記のような製法で製造した塩化ビニル系樹脂水性分散液に、多価アルコールと水溶性亜鉛化合物からなる水溶性の艶消し成分を配合して得ることができるが、得られた組成物は、その構成成分が均質に分散したものであるため、このものを噴霧乾燥すれば、成分均質な粉粒体が得られる。
従って、このペースト用塩化ビニル系樹脂組成物の粉粒体をペースト加工に使用すると、従来にない優れた艶消し性のある製品が得られる。
また、ペースト加工における、プラスチゾルの調製は、ペースト用塩化ビニル系樹脂組成物と可塑剤や添加剤等の配合剤とを混合し、均一に分散させることが必要である。なぜならば、分散が不十分であると、混合バッチ毎に粘度が異なったり、貯蔵中に分散が進行するために粘度変動が大きくなるという問題が発生するだけではなく、成形品の表面の平滑性が悪くなる等の物性が低下することになる。
ところが、本ペースト用塩化ビニル系樹脂組成物の成分は、非常によく分散している点に特性を有するものであるから、当然、本プラスチゾルの調製における分散性は極めて高いものとなる。
従って、本発明のものは、製品の艶消し性に優れているばかりでなく、上記のような問題が発生しない点においても優れている。
A feature of the present invention is that it is versatile by blending specific amounts of two kinds of compounds, that is, a polyhydric alcohol and a water-soluble zinc compound, as a matting component with respect to the vinyl chloride polymer. It is in the point which obtained the vinyl chloride-type resin composition for pastes which exhibits the outstanding mattness.
Both the polyhydric alcohol and the water-soluble zinc compound, which are the matting components of the present invention, are water-soluble, so the affinity of both compounds is extremely good, and it is homogeneous in the aqueous dispersion of vinyl chloride resin. It has the property of dispersing.
The vinyl chloride resin for paste is usually obtained as an aqueous dispersion by an emulsion polymerization method or a microsuspension polymerization method using an aqueous medium containing an emulsifier, but the matte component of the present invention is water-soluble. Because of its affinity with the dispersion, the matting component has the advantage that even when blended with the produced vinyl chloride resin dispersion as it is, it is homogeneously dispersed and exhibits a particular matting effect. .
Therefore, the vinyl chloride resin composition for pastes of the present invention contains a water-soluble matting component comprising a polyhydric alcohol and a water-soluble zinc compound in a vinyl chloride resin aqueous dispersion produced by the above-described method. However, since the obtained composition is a composition in which the constituent components are homogeneously dispersed, if the composition is spray-dried, a granular material having a uniform component can be obtained.
Therefore, when the granular material of the vinyl chloride resin composition for paste is used for paste processing, an unprecedented matte product can be obtained.
In addition, the preparation of plastisol in paste processing requires that the vinyl chloride resin composition for paste and compounding agents such as plasticizers and additives are mixed and uniformly dispersed. This is because, if the dispersion is insufficient, not only will the viscosity be different from one batch to another, or the dispersion will progress during storage, resulting in a large viscosity fluctuation, as well as the smoothness of the surface of the molded product. The physical properties such as worsening will be reduced.
However, since the components of the vinyl chloride resin composition for pastes have characteristics in that they are very well dispersed, naturally, the dispersibility in the preparation of the present plastisol is extremely high.
Therefore, the thing of this invention is excellent not only in the mat | matte property of a product but in the point which the above problems do not generate | occur | produce.
更に、塩化ビニル系樹脂からなる製品、例えば、壁紙等は光沢のない艶消し製品が好まれ、艶消し剤により表面処理を施した製品もあるが、ロータリースクリーン印刷法で製造されることが多い。
ロータリースクリーン印刷法は、回転する円筒状スクリーンの内部にゾルを供給し、スキジーでスクリーンメッシュ開口部からゾルを押し出し、紙等に転写する方法であって、転写後、加熱発泡させて凹凸模様を形成して、壁紙等の製品とされる。
ところが、このロータリースクリーン印刷法により壁紙等の製品を製造する場合、表面処理が困難なため、ゾル又はレジン自身に艶消し性能を備えることが求められる。
本発明のペースト用塩化ビニル系樹脂組成物は、上記の艶消し性能に対する要求に、十分答えることができるので、ロータリースクリーン印刷法による艶消し製品の製造に最適である。
Further, products made of vinyl chloride resin, for example, wallpaper, etc. are preferred to have a matte product with no gloss, and some products have been surface treated with a matting agent, but are often produced by a rotary screen printing method. .
The rotary screen printing method is a method in which a sol is supplied into a rotating cylindrical screen, and the sol is extruded through a screen mesh opening with a squeegee and transferred to paper or the like. Formed into products such as wallpaper.
However, when products such as wallpaper are produced by this rotary screen printing method, the surface treatment is difficult, and therefore the sol or resin itself is required to have a matte performance.
Since the vinyl chloride resin composition for paste of the present invention can sufficiently meet the above-mentioned demand for matting performance, it is optimal for the production of matte products by the rotary screen printing method.
本発明において、このように優れた特性のペースト用塩化ビニル系樹脂組成物が得られた理由は、塩化ビニル系樹脂の水性分散液中に、水溶性の艶消し成分である多価アルコールと水溶性亜鉛化合物が均質に分散する結果、両化合物の艶消し特性が、相乗効果をもって発揮されたためと推察される。
何れにしても、本発明では、塩化ビニル系重合体に対して、艶消し成分として、多価アルコールと水溶性亜鉛化合物を特定量配合することにより、従来にない、汎用性のある優れた特性のペースト用塩化ビニル系樹脂組成物を得ることができたところからみて、本発明の艶消し成分の選択には格別の意義があることは明白である。
In the present invention, the reason why the vinyl chloride resin composition for paste having such excellent characteristics was obtained was that the water-soluble matte component polyhydric alcohol and water-soluble were added to the aqueous dispersion of the vinyl chloride resin. As a result of the homogeneous dispersion of the functional zinc compound, it is presumed that the matte properties of both compounds were exerted with a synergistic effect.
In any case, in the present invention, by adding a specific amount of polyhydric alcohol and water-soluble zinc compound as matting components to the vinyl chloride polymer, unprecedented and versatile excellent characteristics In view of the fact that the vinyl chloride resin composition for pastes can be obtained, the selection of the matting component of the present invention is clearly significant.
以下、本発明について、更に詳述する。
本発明のペースト用塩化ビニル系樹脂組成物は、塩化ビニル系重合体と多価アルコール及び水溶性亜鉛化合物からなる艶消し成分とから構成されるものである。
そこで、本ペースト用塩化ビニル系樹脂組成物の構成成分、製造法、その用途等について、以下説明する。
Hereinafter, the present invention will be described in further detail.
The vinyl chloride resin composition for paste of the present invention comprises a vinyl chloride polymer and a matting component comprising a polyhydric alcohol and a water-soluble zinc compound.
Then, the component of this vinyl chloride-type resin composition for pastes, a manufacturing method, its use, etc. are demonstrated below.
１．ペースト用塩化ビニル系樹脂組成物
（１）構成成分
本発明のペースト用塩化ビニル系樹脂組成物は、以下の塩化ビニル系重合体及び艶消し成分からなるものである。
１）塩化ビニル系重合体
本発明で用いられる塩化ビニル系樹脂は、塩化ビニル単独重合体のほか、塩化ビニルを主としこれと共重合可能な単量体との共重合体である。
塩化ビニルと共重合可能な単量体としては、酢酸ビニル、カプロン酸ビニルなどの炭素数２〜１８のビニルエステル類；アクリル酸、マレイン酸などの不飽和カルボン酸類；メタアクリル酸メチル、マレイン酸モノメチルなどの不飽和カルボン酸エステル類；エチレン、１−ペンテンなどのオレフィン類；アリルグリシジルエーテル、グリシジルメタアクリレートなどのエポキシ基含有不飽和化合物；イソブチルビニルエーテル、オクチルビニルエーテルなどのビニルエーテル類；アクリルニトリル；塩化ビニリデンなどが挙げられる。共重合体にあっては、塩化ビニルは５０重量％以上含有されることが好ましい。
本発明で用いられる塩化ビニル系樹脂は、塩化ビニルまたは塩化ビニルとこれと共重合可能な不飽和単量体とからなる単量体混合物を、乳化重合（播種乳化重合を含む）または微細懸濁重合（播種微細懸濁重合を含む）することによって得られる。
乳化重合は、水を媒体とし、アニオン性界面活性剤、水溶性の重合開始剤を用い、塩化ビニルなどの単量体を可溶化したアニオン界面活性剤ミセル内で重合を進め、粒径０．０５〜０．５μｍの範囲内のシャープなモードを有する粒径分布の微小球形重合体粒子のラテックスを得る重合法である。
播種乳化重合法は、乳化重合により得られた重合体を種子として、水媒体中でこれに単量体を被覆重合して肥大化させる重合法で、重合体粒子を安定化するためのアニオン性界面活性剤を、重合体粒子表面を覆うに必要な量以上とならないように重合反応の進行に調和させて添加しつつ水溶性の重合開始剤で重合反応を行う方法である。通常、一次粒子の粒径は、０．９〜１．３μｍの肥大化された主たる粒子群と、０．１〜０．３μｍの少量の副生粒子群とからなる２つのモードを有する重合体を含有するラテックスが得られる。
微細懸濁重合は、水媒体中で単量体を油溶性重合開始剤の存在下、アニオン性界面活性剤を乳化剤として用いてホモジナイザにより均質化し、単量体の乳化液滴を比較的緩かな撹拌下で重合して重合体に転化せしめるもので、通常、一次粒子は０．０５〜５μｍのブロードな山形の粒径分布を持つ球形の重合体粒子を含有するラテックスが得られる。
なお、前記乳化重合または微細懸濁重合において、粒子の安定化や粒径調整のために、アニオン性界面活性剤の他に、高級アルコール、ソルビタンステアリルエステルなどの親油性の補助乳化剤を添加することも可能である。
上記の重合法により、塩化ビニル系重合体は水性分散液として得られる。
1. Vinyl chloride resin composition for paste (1) Component The vinyl chloride resin composition for paste of the present invention comprises the following vinyl chloride polymer and matting component.
1) Vinyl chloride polymer The vinyl chloride resin used in the present invention is not only a vinyl chloride homopolymer but also a copolymer of vinyl chloride as a main component and a copolymerizable monomer.
Monomers copolymerizable with vinyl chloride include vinyl esters having 2 to 18 carbon atoms such as vinyl acetate and vinyl caproate; unsaturated carboxylic acids such as acrylic acid and maleic acid; methyl methacrylate, maleic acid Unsaturated carboxylic acid esters such as monomethyl; olefins such as ethylene and 1-pentene; epoxy group-containing unsaturated compounds such as allyl glycidyl ether and glycidyl methacrylate; vinyl ethers such as isobutyl vinyl ether and octyl vinyl ether; acrylonitrile; Examples include vinylidene. In the copolymer, vinyl chloride is preferably contained in an amount of 50% by weight or more.
The vinyl chloride resin used in the present invention is obtained by emulsion polymerization (including seeding emulsion polymerization) or fine suspension of vinyl chloride or a monomer mixture comprising vinyl chloride and an unsaturated monomer copolymerizable therewith. It is obtained by polymerization (including seeding fine suspension polymerization).
Emulsion polymerization uses water as a medium, an anionic surfactant and a water-soluble polymerization initiator, and proceeds in an anionic surfactant micelle solubilized with a monomer such as vinyl chloride. This is a polymerization method for obtaining a latex of fine spherical polymer particles having a particle size distribution having a sharp mode in the range of from 0.5 to 0.5 μm.
The seeding emulsion polymerization method is a polymerization method in which a polymer obtained by emulsion polymerization is used as a seed, and a monomer is coated and polymerized in an aqueous medium to enlarge the polymer, and anionic properties for stabilizing polymer particles. This is a method of performing a polymerization reaction with a water-soluble polymerization initiator while adding a surfactant in accordance with the progress of the polymerization reaction so as not to exceed the amount necessary to cover the surface of the polymer particles. Usually, the primary particle has a particle size of 0.9 to 1.3 μm, a main particle group enlarged and a small amount of a by-product particle group of 0.1 to 0.3 μm and a polymer having two modes. A latex containing is obtained.
In the fine suspension polymerization, the monomer is homogenized by a homogenizer using an anionic surfactant as an emulsifier in the presence of an oil-soluble polymerization initiator in an aqueous medium. The polymer is polymerized under stirring to be converted into a polymer, and usually a latex containing spherical polymer particles having a broad chevron particle size distribution of 0.05 to 5 μm is obtained as the primary particles.
In addition, in the emulsion polymerization or fine suspension polymerization, a lipophilic auxiliary emulsifier such as a higher alcohol or sorbitan stearyl ester is added in addition to the anionic surfactant for particle stabilization and particle size adjustment. Is also possible.
By the above polymerization method, the vinyl chloride polymer is obtained as an aqueous dispersion.
２）艶消し成分
本発明の艶消し成分は、多価アルコール及び水溶性亜鉛化合物からなる化合物を特定量、併用する点に特徴を有する。
本艶消し成分は、水溶性成分からなるので、上記の方法で製造された塩化ビニル系重合体の水性分散液に親和性がある。
従って、目的のペースト用塩化ビニル系樹脂組成物を得るため、本発明の艶消し成分と塩化ビニル系重合体の水性分散液とを配合した場合、親和性がよいので、艶消し成分は均質に分散して存在することになる。その結果、本発明の艶消し成分の配合により、本ペースト用塩化ビニル系樹脂組成物は優れた艶消し特性を有するものとなる。
以下、本発明の艶消し成分である、多価アルコール及び水溶性亜鉛化合物について、述べる。
2) Matting component The matting component of the present invention is characterized in that a specific amount of a compound comprising a polyhydric alcohol and a water-soluble zinc compound is used in combination.
Since the matting component comprises a water-soluble component, it has an affinity for an aqueous dispersion of a vinyl chloride polymer produced by the above method.
Therefore, in order to obtain the desired vinyl chloride resin composition for paste, when the matting component of the present invention and the aqueous dispersion of the vinyl chloride polymer are blended, the matting component is homogeneous because the affinity is good. It will be distributed. As a result, the vinyl chloride resin composition for pastes has excellent matting characteristics due to the blending of the matting component of the present invention.
The polyhydric alcohol and water-soluble zinc compound, which are the matting components of the present invention, will be described below.
（ａ）多価アルコール
本発明の多価アルコールは、１分子中に２個以上の水酸基を有する化合物であるが、その種類は問わない。例えば、グリセリン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール等が挙げられる。
多価アルコールの使用量は、塩化ビニル系重合体１００重量部に対し、０．２〜５重量部、好ましくは０．５〜３重量部である。使用量が０．２重量部未満の場合は、充分な艶消し効果が得られず、また５重量部を越えた場合は、添加量の割りには艶消し改良効果が少なく、経済的ではない。
(A) Polyhydric alcohol Although the polyhydric alcohol of this invention is a compound which has a 2 or more hydroxyl group in 1 molecule, the kind is not ask | required. Examples thereof include glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like.
The amount of polyhydric alcohol used is 0.2 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride polymer. When the amount used is less than 0.2 parts by weight, a sufficient matting effect cannot be obtained, and when it exceeds 5 parts by weight, the matte improvement effect is small for the amount of addition, which is not economical. .
（ｂ）水溶性亜鉛化合物
本発明の水溶性亜鉛化合物は、水溶性の亜鉛化合物であれば、その種類は特に問わない。本発明の亜鉛化合物は、水溶性のものであることが必須の要件であり、油溶性のものでは、所期の目的は達成できない。
水溶性亜鉛化合物としては、無機酸の亜鉛塩が好ましく、例えば、塩化亜鉛、硫酸亜鉛、硝酸亜鉛等が挙げられる。
水溶性亜鉛化合物の使用量は、塩化ビニル系重合体１００重量部に対し、０．２〜５重量部、好ましくは０．５〜５重量部である。使用量が０．２重量部未満の場合は、充分な艶消し効果が得られず、また５重量部を越えた場合は、添加量の割りには艶消し改良効果が少なく、経済的ではない。
(B) Water-soluble zinc compound The water-soluble zinc compound of the present invention is not particularly limited as long as it is a water-soluble zinc compound. It is an essential requirement that the zinc compound of the present invention is water-soluble, and if it is oil-soluble, the intended purpose cannot be achieved.
As the water-soluble zinc compound, a zinc salt of an inorganic acid is preferable, and examples thereof include zinc chloride, zinc sulfate, and zinc nitrate.
The amount of the water-soluble zinc compound used is 0.2 to 5 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride polymer. When the amount used is less than 0.2 parts by weight, a sufficient matting effect cannot be obtained, and when it exceeds 5 parts by weight, the matte improvement effect is small for the amount of addition, which is not economical. .
（製法）
本発明のペースト用塩化ビニル系樹脂組成物は、塩化ビニル系重合体、多価アルコール及び水溶性亜鉛化合物からなる艶消し成分から構成されている限り、その製法や形態等は、特に限定されない。
本組成物の製法としては、塩化ビニル系重合体の水性分散液に、艶消し成分（多価アルコール及び水溶性亜鉛化合物）を存在させる方法を用いるのがよい。
このような方法としては、例えば、塩化ビニル系樹脂の重合時の水性媒体中に、予め、艶消し成分の多価アルコール及び水溶性亜鉛化合物の両者或いは一方を添加混合する方法、又は重合後の塩化ビニル系重合体の水性分散液中に、両者或いは一方を添加混合する方法等が挙げられる。
上記の方法によると、塩化ビニル系重合体の分散液と艶消し成分の親和性が高いため、両者の混合物を単に攪拌するだけで、各成分が容易に均一に分散することができるので、有利である。
そして、このようにして得た、塩化ビニル系重合体、多価アルコール及び水溶性亜鉛化合物の３成分からなる水性分散液は、噴霧乾燥することにより、粉粒体の形態とすることができる。
また、艶消し成分である多価アルコール及び水溶性亜鉛化合物を、プラスチゾル調製時に、通常のペースト用塩化ビニル系樹脂組成物に配合して、プラスチゾルを製造することも可能である。
(Manufacturing method)
As long as the vinyl chloride resin composition for paste of the present invention is composed of a matting component comprising a vinyl chloride polymer, a polyhydric alcohol and a water-soluble zinc compound, its production method, form, etc. are not particularly limited.
As a method for producing this composition, it is preferable to use a method in which a matting component (polyhydric alcohol and water-soluble zinc compound) is present in an aqueous dispersion of a vinyl chloride polymer.
As such a method, for example, in the aqueous medium at the time of polymerization of the vinyl chloride resin, a method in which both or one of the polyhydric alcohol and water-soluble zinc compound as a matting component are added and mixed in advance, or after polymerization Examples thereof include a method in which both or one is added and mixed in an aqueous dispersion of a vinyl chloride polymer.
According to the above method, since the affinity between the dispersion of the vinyl chloride polymer and the matting component is high, each component can be easily and uniformly dispersed by simply stirring the mixture of the two. It is.
The aqueous dispersion composed of the three components of the vinyl chloride polymer, the polyhydric alcohol, and the water-soluble zinc compound thus obtained can be made into a granular form by spray drying.
It is also possible to produce a plastisol by blending a polyhydric alcohol, which is a matting component, and a water-soluble zinc compound, with a normal vinyl chloride resin composition for pastes when preparing the plastisol.
（２）配合剤
本ペースト用塩化ビニル系樹脂組成物は、通常、粉粒体の形で得られるが、このものと配合剤とを配合することにより、ペースト加工用原料を効率的に得ることができる。
配合剤としては、以下のものが挙げられる。
１）可塑剤
本発明に用いられる可塑剤は、塩化ビニルプラスチゾルに使用される可塑剤であればいずれでもよく、特に制限なく使用される。
具体的には、ジブチルフタレート、ジ−（２−エチルヘキシル）フタレート、ジ−ｎ−オクチルフタレート、ジイソブチルフタレート、ジヘプチルフタレート、ジフェニルフタレート、ジイソデシルフタレート、ジウンデシルフタレート、ブチルベンジルフタレートなどのフタル酸誘導体；ジ−（２−エチルヘキシル）イソフタレート、ジイソオクチルイソフタレートなどのイソフタル酸誘導体；ジ−ｎ−ブチルアジペート、ジ−（２−エチルヘキシル）アジペート、ジイソデシルアジペート、ジイソノニルアジペートなどのアジピン酸誘導体；ジ−（２−エチルヘキシル）アゼレート、ジイソオクチルアゼレート、ジ−ｎ−ヘキシルアゼレートなどのアゼライン酸誘導体；ジ−ｎ−ブチルセバケート、ジ−（２−エチルヘキシル）セバケートなどのセバシン酸誘導体；ジ−ｎ−ブチルマレエート、ジメチルマレエート、ジエチルマレエート、ジ−（２−エチルヘキシル）マレエートなどのマレイン酸誘導体；ジ−ｎ−ブチルフマレート、ジ−（２−エチルヘキシル）フマレートなどのフマル酸誘導体；トリ−（２−エチルヘキシル）トリメリテート、トリ−ｎ−オクチルトリメリテート、トリイソオクチルトリメリテート、トリ−ｎ−ヘキシルトリメリテートなどのトリメリット酸誘導体；テトラ−（２−エチルヘキシル）ピロメリテート、テトラ−ｎ−オクチルピロメリテートなどのピロメリット酸誘導体；トリエチルシトレート、アセチルトリエチルシトレート、アセチルトリ−（２−エチルヘキシル）シトレートなどのクエン酸誘導体；モノメチルイタコネート、モノブチルイタコネート、ジメチルイタコネート、ジエチルイタコネート、ジブチルイタコネートなどのイタコン酸誘導体；ブチルオレエート、グリセリルモノオレエート、ジエチレングリコールモノオレエートなどのオレイン酸誘導体；グリセリルモノリシノレート、ジエチレングリコールモノリシノレートなどのリシノール酸誘導体；グリセリンモノステアレート、ジエチレングリコールジステアレートなどのステアリン酸誘導体；ジエチレングリコールモノラウレート、ジエチレングリコールジペラルゴネート、ペンタエリスリトール脂肪酸エステルなどのその他の脂肪酸誘導体；トリブチルホスフェート、トリ−（２−エチルヘキシル）ホスフェート、トリフェニルホスフェート、トリクレジルホスフェートなどのリン酸誘導体；ジエチレングリコールジベンゾエート、ジプロピレングリコールジベンゾエート、ジブチルメチレンビスチオグリコレートなどのグリコール誘導体；グリセロールモノアセテート、グリセロールトリアセテート、グリセロールトリブチレートなどのグリセリン誘導体；アジピン酸系ポリエステル、セバシン酸系ポリエステル、フタル酸系ポリエステルなどのポリエステル系可塑剤；ジアリルフタレート、アクリル系モノマーやオリゴマーなどの重合性可塑剤などが挙げられるが、これらの中でフタル酸エステル系のものが好適である。これらの可塑剤は１種用いてもよいし、２種以上を組み合わせて用いてもよい。
可塑剤の配合量は、塩化ビニル樹脂１００重量部当たり、３０〜３００重量部の範囲で選ばれ、５０〜２００重量部が好ましい。可塑剤が３０重量部より少ないとプラスチゾルの粘度が高くなり、加工が困難になる可能性があり、逆に３００重量部より多いと成型品が柔らかくなり、形状が安定しなくなる恐れがある。
(2) Compounding agent The vinyl chloride resin composition for the present paste is usually obtained in the form of a granular material. By blending this with a compounding agent, a paste processing raw material can be obtained efficiently. Can do.
The following are mentioned as a compounding agent.
1) Plasticizer The plasticizer used in the present invention may be any plasticizer used for vinyl chloride plastisol, and is used without particular limitation.
Specifically, phthalic acid derivatives such as dibutyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, diundecyl phthalate, butyl benzyl phthalate; Isophthalic acid derivatives such as di- (2-ethylhexyl) isophthalate and diisooctylisophthalate; adipic acid derivatives such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, diisodecyl adipate and diisononyl adipate; Azelaic acid derivatives such as (2-ethylhexyl) azelate, diisooctylazelate, di-n-hexylazelate; di-n-butyl sebacate, di- (2-ethylhexyl) sebacate Sebacic acid derivatives such as: di-n-butyl maleate, dimethyl maleate, diethyl maleate, maleic acid derivatives such as di- (2-ethylhexyl) maleate; di-n-butyl fumarate, di- (2-ethylhexyl) ) Fumaric acid derivatives such as fumarate; trimellitic acid derivatives such as tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, tri-n-hexyl trimellitate; tetra- Pyromellitic acid derivatives such as (2-ethylhexyl) pyromellitate and tetra-n-octyl pyromellitate; citric acid derivatives such as triethyl citrate, acetyl triethyl citrate and acetyl tri- (2-ethylhexyl) citrate; monomethyl itaconate, Monochuchi Itaconic acid derivatives such as itaconate, dimethyl itaconate, diethyl itaconate and dibutyl itaconate; oleic acid derivatives such as butyl oleate, glyceryl monooleate and diethylene glycol monooleate; ricinol such as glyceryl monoricinoleate and diethylene glycol monoricinoleate Acid derivatives; stearic acid derivatives such as glycerin monostearate and diethylene glycol distearate; other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate and pentaerythritol fatty acid ester; tributyl phosphate, tri- (2-ethylhexyl) phosphate , Triphenyl phosphate, tricresyl phosphate and other phosphoric acid derivatives; Glycol derivatives such as recall dibenzoate, dipropylene glycol dibenzoate, dibutylmethylene bisthioglycolate; glycerol derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate; adipic acid polyester, sebacic acid polyester, phthalic acid Polyester plasticizers such as polyesters; diallyl phthalates, polymerizable plasticizers such as acrylic monomers and oligomers, and the like. Among these, phthalate ester-based ones are preferred. These plasticizers may be used alone or in combination of two or more.
The compounding quantity of a plasticizer is chosen in the range of 30-300 weight part per 100 weight part of vinyl chloride resins, and 50-200 weight part is preferable. If the amount of the plasticizer is less than 30 parts by weight, the viscosity of the plastisol becomes high and processing may become difficult. Conversely, if the amount is more than 300 parts by weight, the molded product becomes soft and the shape may not be stable.
２）発泡剤
本発明のペースト用塩化ビニル系樹脂組成物を用いて、その成形を発泡成形とするには、更に発泡剤を含有させる。
発泡剤としては、例えば、アゾジカルボンアミド、アゾビスイソプチロニトリル、ジニトロソペンタメチレンテトラミン、４，４’−オキシビスベンゼンスルホニルヒドラジド、パラトルエンスルホニルヒドラジド等が挙げられる。
発泡剤は２種以上混合して使用することもできる。更に、発泡剤の分解温度も低下させる目的で使用される発泡助剤も含有することができる。発泡剤の使用量は、塩化ビニル系重合体１００重量部に対して、通常、６重量部以下、好ましくは４重量部以下である。
2) Foaming agent In order to make the molding into foam molding using the vinyl chloride resin composition for paste of the present invention, a foaming agent is further contained.
Examples of the foaming agent include azodicarbonamide, azobisisoptyronitrile, dinitrosopentamethylenetetramine, 4,4′-oxybisbenzenesulfonyl hydrazide, paratoluenesulfonyl hydrazide, and the like.
Two or more foaming agents can be used in combination. Furthermore, a foaming aid used for the purpose of lowering the decomposition temperature of the foaming agent can also be contained. The amount of the foaming agent used is usually 6 parts by weight or less, preferably 4 parts by weight or less with respect to 100 parts by weight of the vinyl chloride polymer.
３）添加剤
本発明で用いられる添加剤としては、例えば、シリカ、タルク、クレイ、ケイソウ土、マイカ、水酸化アルミニウム、アルミナなどが挙げられるが、更に、チタン白（酸化チタン）、カドミウムイエロー（硫化カドミウム）、クロムイエロー（クロム酸鉛）、チモノックス（三酸化アンチモン）、ホワイト鉛（塩基性炭酸鉛）、ベンガラ（三二酸化鉄）などの無機顔料；三酸化アンチモンなどの無機難燃化剤；珪酸カルシウム、シリカアエロジルなどの無機ゲル化剤；酸化亜鉛などの無機キッカーなどの無機充填剤が挙げられる。
無機充填剤の配合量は、塩化ビニル樹脂１００重量部に対して８０〜２２０重量部、好ましくは１００〜２００重量部、更に好ましくは１５０〜１８０重量部が使用される。無機充填剤の配合量が８０重量部以上であるのは、本発明のプラスチゾル組成物が無機充填剤を多量に含有される塩化ビニルプラスチゾル発泡体の成形不良を解決するための組成物であるからであり、一方、無機充填剤の配合量が２２０重量部以下であるのは、それより多いと発泡体の強度が低下して破損しやすくなる可能性があるからである。
また、熱及び光安定剤、例えば、オクタン酸亜鉛、ステアリン酸カルシウム又は亜鉛塩、オクタン酸カドミウム、リシノール酸バリウム、等も添加することができる。
3) Additives Examples of the additive used in the present invention include silica, talc, clay, diatomaceous earth, mica, aluminum hydroxide, alumina, and the like. Further, titanium white (titanium oxide), cadmium yellow ( Inorganic pigments such as cadmium sulfide), chrome yellow (lead chromate), timonox (antimony trioxide), white lead (basic lead carbonate), bengara (iron sesquioxide); inorganic flame retardants such as antimony trioxide; Examples thereof include inorganic gelling agents such as calcium silicate and silica aerosil; and inorganic fillers such as inorganic kickers such as zinc oxide.
The blending amount of the inorganic filler is 80 to 220 parts by weight, preferably 100 to 200 parts by weight, and more preferably 150 to 180 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. The blending amount of the inorganic filler is 80 parts by weight or more because the plastisol composition of the present invention is a composition for solving the molding failure of the vinyl chloride plastisol foam containing a large amount of the inorganic filler. On the other hand, the blending amount of the inorganic filler is 220 parts by weight or less because if it is more than that, the strength of the foam may be reduced and the foam may be easily damaged.
Heat and light stabilizers such as zinc octoate, calcium stearate or zinc salts, cadmium octoate, barium ricinoleate, and the like can also be added.
（３）用途
本ペースト用塩化ビニル系樹脂組成物からの製品の製造は、先ずプラスチゾルを調製し、次いで成形（賦形）した後、ゲル化し、続いてこれを加熱溶融し、次いで冷却して、目的の成形体とする方法により行われる。以下、この点について説明する。
１）プラスチゾルの調製
プラスチゾルの調製は、ペースト用塩化ビニル系樹脂組成物と可塑剤や添加剤等の配合剤とを混合し、均一に分散させることが必要である。
なぜならば、前述したように、分散が不十分であると、混合バッチ毎に粘度が異なったり、貯蔵中に分散が進行するために粘度変動が大きくなるという問題が発生するだけではなく、成形品の表面の平滑性が悪くなる等の物性が低下することになる。
前述したように、本ペースト用塩化ビニル系樹脂組成物の成分は、非常によく分散している点に特徴を有するものであるから、当然、本プラスチゾルの調製における分散性は極めて高いものとなる。
プラスチゾル調製用の混合機としては、通常のもの、例えば、一軸ディゾルバー、二軸ミキサー、バタフライ、ポニー、ホバートミキサー等が用いられる。
(3) Use The manufacture of the product from the vinyl chloride resin composition for the present paste involves first preparing a plastisol, then forming (shaping), gelling, subsequently heating and melting, and then cooling. It is carried out by a method of obtaining a desired molded body. Hereinafter, this point will be described.
1) Preparation of plastisol Preparation of plastisol requires that a vinyl chloride resin composition for paste and a compounding agent such as a plasticizer or an additive are mixed and uniformly dispersed.
This is because, as described above, insufficient dispersion not only causes the problem that the viscosity varies from one batch to another, or the viscosity fluctuates greatly because the dispersion proceeds during storage. The physical properties such as poor surface smoothness will be reduced.
As described above, since the components of the vinyl chloride resin composition for the paste are characterized by being very well dispersed, of course, the dispersibility in the preparation of the plastisol is extremely high. .
As a mixer for preparing plastisol, an ordinary one, for example, a uniaxial dissolver, a biaxial mixer, a butterfly, a pony, a Hobart mixer, or the like is used.
２）成形法
賦形のための成形法としては、製品に応じ、種々の方法を用いることができる。
例えば、コーティング成形法、ディッピング成形法、スラッシュ成形法、注型成形法、回転成形法等が挙げられる。
上記の方法で賦形された成形体は、加熱してゲル化させ、形を固定する。加熱方法は、通常の方法、例えば、オーブン、トンネル型加熱炉等により行う。温度は、用いる樹脂に合わせて、１２０〜１５０℃程度とする。
続いて、ゲル化させた成形体を１６０〜２５０℃に加熱溶融させ、次いで冷却して、最終製品とする。
2) Molding method As the molding method for shaping, various methods can be used depending on the product.
For example, a coating molding method, a dipping molding method, a slush molding method, a casting molding method, a rotational molding method and the like can be mentioned.
The molded body shaped by the above method is heated to be gelled and fixed in shape. The heating method is performed by a normal method, for example, an oven, a tunnel type heating furnace or the like. The temperature is about 120 to 150 ° C. according to the resin used.
Subsequently, the gelled molded body is heated and melted to 160 to 250 ° C. and then cooled to obtain a final product.
（４）製品
上記の成形法により種々の製品を製造することができる。例えば、以下のものが挙げられる。
コーティング成形（床材、壁材、鋼板、レザー、フィルム等、ディッピング成形（電気部品、工業部品、手袋、雑貨等）、スラッシュ成形（ブーツ、玩具、自動車内装材等）、注型成形（缶シール、食品サンプル等）、回転成形（自動車内装材、玩具等）。
(4) Products Various products can be produced by the above molding method. For example, the following are mentioned.
Coating molding (floor materials, wall materials, steel plates, leather, films, etc.) Dipping molding (electrical parts, industrial parts, gloves, miscellaneous goods, etc.), slush molding (boots, toys, automotive interior materials, etc.), cast molding (can seals) , Food samples, etc.), rotational molding (automobile interior materials, toys, etc.).
（１）本発明のペースト用塩化ビニル系樹脂組成物は、各成分が非常によく分散しているのため、艶消し特性が非常に優れているとともに、得られた製品の表面の平滑性が悪くなることもなく、物性の低下もない。
（２）表面処理が困難なため、ゾル又はレジン自身に艶消し特性が求められるところの、ロータリースクリーン印刷法による艶消し製品の製造においても、全く問題が発生しないので、これら製品の製造に特に最適である。
（３）ペースト用塩化ビニル系樹脂は、通常、乳化剤を含んだ水性媒体を用いた乳化重合法やミクロ懸濁重合法により、水性分散液として得られるが、本発明の艶消し成分は水溶性であって、該分散液と親和性があるので、本発明の艶消し成分は、製造された塩化ビニル系樹脂分散液とそのまま配合しても、均質に分散し、特段の艶消し効果を発揮するという利点がある。
（４）本発明のペースト用塩化ビニル系樹脂組成物は、噴霧乾燥すると、簡単に各成分が均質に分散された粉粒体となるので、該粉粒体を成形加工に利用すると、優れた艶消し特性の製品を簡便に得ることができる。
(1) The vinyl chloride resin composition for paste according to the present invention has excellent matting properties and smoothness of the surface of the product obtained because each component is very well dispersed. There will be no deterioration and no deterioration in physical properties.
(2) Since surface treatment is difficult, matte properties are required for the sol or resin itself, but no problem occurs in the production of matte products by the rotary screen printing method. Is optimal.
(3) The vinyl chloride resin for paste is usually obtained as an aqueous dispersion by emulsion polymerization or microsuspension polymerization using an aqueous medium containing an emulsifier, but the matte component of the present invention is water-soluble. Since it has an affinity for the dispersion, the matting component of the present invention is homogeneously dispersed even when blended with the produced vinyl chloride resin dispersion as it is, and exhibits a special matting effect. There is an advantage of doing.
(4) The vinyl chloride resin composition for paste according to the present invention, when spray-dried, easily becomes a granular material in which each component is uniformly dispersed. Therefore, when the granular material is used for molding, it is excellent. Products with matte properties can be obtained easily.
以下、実施例等を挙げて本発明を更に詳細に説明するが、本発明はこれらのものに限定されない。なお、「部」は、特に断らない限り、「重量部」を意味する。
実施例等の物性測定は、下記の方法で行った。
＜艶消し性＞
日本電色工業（株）製、変角光沢計（ＶＧ−１Ｄ）を用い、６０°反射率（グロス）％の値を測定し、評価した。この値が小さいほど、表面光沢が少なく、艶消し性は良好である。
Hereinafter, although an example etc. are given and the present invention is explained still in detail, the present invention is not limited to these. “Part” means “part by weight” unless otherwise specified.
The physical properties of Examples and the like were measured by the following methods.
<Matte property>
Using a variable angle gloss meter (VG-1D) manufactured by Nippon Denshoku Industries Co., Ltd., the value of 60 ° reflectance (gloss)% was measured and evaluated. The smaller this value, the less the surface gloss and the better the matte properties.
＜表面の平滑性＞
目視により行い、以下の５段階評価とした。
◎：非常に表面が平滑
○：僅かに小さな凸凹がある
△：全体的に小さな凸凹がある
×：小さな凹凸に加え、僅かに大きな凹凸がある
××：全体的に大きな凹凸がある
<Surface smoothness>
The following five-step evaluation was performed by visual inspection.
A: Extremely smooth surface B: Slightly small irregularities Δ: Overall small irregularities ×: Small irregularities in addition to slightly irregularities XX: Overall large irregularities
（実施例１）
＜重合＞
１００Ｌのグラスライニング製オートクレーブを脱気し、脱イオン水４０kg、塩化ビニル単量体１６kg、ラウリル硫酸ナトリウム１４０ｇ、ステアリルアルコール２４０g、ジ−2−エチルへキシルパーオキシジカーボネート７．５ｇを仕込み、ホモジナイザーで均質化処理後、４９℃まで昇温して重合を開始した。反応器内の圧力が０．０５ＭＰａ低下した時点で重合を止め、未反応単量体を回収し、塩化ビニル樹脂の水性分散液を得た。
＜ペースト用樹脂組成物の調製＞
得られた塩化ビニル樹脂の水性分散液に、塩化ビニル重合体１００部当たり、ラウリル硫酸ナトリウム０．４部、ポリオキシエチレンアルキルエーテル０．４部、トリメチロールプロパン０．８部および塩化亜鉛１．０部を添加し、撹拌均一化した後、スプレードライヤー（ニロ社製ロータリーアトマイザー型）により噴霧乾燥して、塩化ビニル樹脂組成物の粉粒体を得た。
(Example 1)
<Polymerization>
A 100 L glass-lined autoclave was degassed and charged with 40 kg of deionized water, 16 kg of vinyl chloride monomer, 140 g of sodium lauryl sulfate, 240 g of stearyl alcohol, and 7.5 g of di-2-ethylhexylperoxydicarbonate were added to the homogenizer. Then, the temperature was raised to 49 ° C. to initiate polymerization. When the pressure in the reactor dropped by 0.05 MPa, the polymerization was stopped and the unreacted monomer was recovered to obtain an aqueous dispersion of vinyl chloride resin.
<Preparation of resin composition for paste>
In an aqueous dispersion of the obtained vinyl chloride resin, 0.4 part of sodium lauryl sulfate, 0.4 part of polyoxyethylene alkyl ether, 0.8 part of trimethylolpropane and zinc chloride per 100 parts of the vinyl chloride polymer. After adding 0 part and stirring and homogenizing, it was spray-dried with a spray dryer (rotary atomizer type manufactured by Niro Co., Ltd.) to obtain a granular material of a vinyl chloride resin composition.
＜ペーストゾルの調製＞
得られた塩化ビニル樹脂組成物の粉粒体１００部に、可塑剤としてジー２−エチルへキシルフタレート５５部、炭酸カルシウム（白石工業（株）製、ホワイトンＨ）１００部、酸化チタン（デュポン製、Ｒ９００）１５部、発泡剤（大塚化学（株）製、ＡＺＨ−２５）３部、安定剤（共同薬品（株）製、ＫＦ６５Ｊ２）３部、希釈剤５部を加え、ライカイ機にて混練して、ペーストゾルを調製した。
<Preparation of paste sol>
To 100 parts of the granular material of the obtained vinyl chloride resin composition, 55 parts of di-2-ethylhexyl phthalate as a plasticizer, 100 parts of calcium carbonate (Shiraishi Kogyo Co., Ltd., Whiten H), titanium oxide (DuPont) 15 parts made by R900, 3 parts foaming agent (manufactured by Otsuka Chemical Co., Ltd., AZH-25), 3 parts stabilizer (manufactured by Kyodo Pharmaceutical Co., Ltd., KF65J2), 5 parts diluent, The paste sol was prepared by kneading.
＜評価＞
得られたペーストゾルを、ナイフコーターを用いて難燃紙上に１５０μｍの厚みにコートし、１５０℃のオーブンで３０秒間熱処理して塗布面を半ゲル状態とした。冷却後、短冊状に試料を切り、２２０℃のオーブン中で５０秒間熱処理してゲル化させ、艶消し性を評価した。結果を表１に示す。
<Evaluation>
The obtained paste sol was coated to a thickness of 150 μm on a flame retardant paper using a knife coater and heat-treated in an oven at 150 ° C. for 30 seconds to make the coated surface in a semi-gel state. After cooling, the sample was cut into a strip shape and heat-treated in an oven at 220 ° C. for 50 seconds to be gelled, and the matte property was evaluated. The results are shown in Table 1.
（実施例２〜１５）
実施例１のペースト用樹脂組成物の調製工程において、使用する多価アルコールおよび亜鉛化合物を表１に示した種類および量に変えた以外は、実施例１と同様に行った。その結果を表１に示す。
(Examples 2 to 15)
In the preparation process of the resin composition for paste of Example 1, it carried out similarly to Example 1 except having changed the polyhydric alcohol and zinc compound to be used into the kind and quantity shown in Table 1. The results are shown in Table 1.
（実施例１６）
実施例１において、トリメチロールプロパンおよび塩化亜鉛を、ペースト用樹脂組成物の調製工程で配合する代わりに、ペーストゾルの調製工程で配合する以外は、実施例１と同様に行った。その結果を表１に示す。
(Example 16)
In Example 1, it carried out like Example 1 except mix | blending a trimethylolpropane and zinc chloride at the preparation process of a paste sol instead of mix | blending at the preparation process of the resin composition for pastes. The results are shown in Table 1.
（比較例1〜７）
実施例１のペースト用樹脂組成物の調製において、使用する多価アルコールおよび亜鉛化合物を表２に示した種類および量に変えた以外は、実施例１と同様に行った。その結果を表２に示す。
(Comparative Examples 1-7)
The preparation of the resin composition for paste in Example 1 was carried out in the same manner as in Example 1 except that the polyhydric alcohol and zinc compound used were changed to the types and amounts shown in Table 2. The results are shown in Table 2.
表１、２の結果から、塩化ビニル系重合体に対して、艶消し成分として、多価アルコールおよび亜鉛化合物を特定量使用すると、優れた艶消し特性を有するペースト用塩化ビニル系樹脂組成物が得られることが解る。 From the results of Tables 1 and 2, when a specific amount of polyhydric alcohol and zinc compound is used as a matting component for a vinyl chloride polymer, a vinyl chloride resin composition for paste having excellent matting characteristics is obtained. You can see that
本発明のペースト用塩化ビニル系樹脂組成物は、各成分が非常によく分散しているため、艶消し特性が非常に優れているとともに、得られた製品の表面の平滑性が悪くなることもなく、物性の低下もないので、各種の製品に適用可能である。
The vinyl chloride resin composition for paste according to the present invention has very good matting characteristics because each component is very well dispersed, and the smoothness of the surface of the obtained product may be deteriorated. In addition, since there is no deterioration in physical properties, it can be applied to various products.
Claims (6)
A matte product produced from the vinyl chloride resin composition for paste according to claim 1, 2, 3, 4 or 5.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010138306A (en) * | 2008-12-12 | 2010-06-24 | Nippon Zeon Co Ltd | Vinyl chloride-based resin composition for powder molding, vinyl chloride-based resin molded body and laminated body |
| KR101141808B1 (en) | 2009-07-16 | 2012-05-07 | 주식회사 엘지화학 | Manufacturing Method of PVC polymer and PVC copolymer Having Polyol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010138306A (en) * | 2008-12-12 | 2010-06-24 | Nippon Zeon Co Ltd | Vinyl chloride-based resin composition for powder molding, vinyl chloride-based resin molded body and laminated body |
| KR101141808B1 (en) | 2009-07-16 | 2012-05-07 | 주식회사 엘지화학 | Manufacturing Method of PVC polymer and PVC copolymer Having Polyol |
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