TW201815943A - 氯乙烯樹脂組成物、氯乙烯樹脂成形體及堆疊體 - Google Patents
氯乙烯樹脂組成物、氯乙烯樹脂成形體及堆疊體 Download PDFInfo
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- TW201815943A TW201815943A TW106132344A TW106132344A TW201815943A TW 201815943 A TW201815943 A TW 201815943A TW 106132344 A TW106132344 A TW 106132344A TW 106132344 A TW106132344 A TW 106132344A TW 201815943 A TW201815943 A TW 201815943A
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- Prior art keywords
- vinyl chloride
- chloride resin
- silicone oil
- resin composition
- modified silicone
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- YKDMBTQVKVEMSA-UHFFFAOYSA-N diethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOCCOC(=O)CCCCCCCCCCCCCCCCC YKDMBTQVKVEMSA-UHFFFAOYSA-N 0.000 description 1
- 229940111071 diethylene glycol distearate Drugs 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
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- 229960001826 dimethylphthalate Drugs 0.000 description 1
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 1
- UCEHPOGKWWZMHC-UHFFFAOYSA-N dioctyl cyclohex-3-ene-1,2-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1CCC=CC1C(=O)OCCCCCCCC UCEHPOGKWWZMHC-UHFFFAOYSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- YCZJVRCZIPDYHH-UHFFFAOYSA-N ditridecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCCC YCZJVRCZIPDYHH-UHFFFAOYSA-N 0.000 description 1
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- MMBNRPUBYXPHEG-UHFFFAOYSA-N ethenyl propanoate;propanoic acid Chemical compound CCC(O)=O.CCC(=O)OC=C MMBNRPUBYXPHEG-UHFFFAOYSA-N 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000002237 fumaric acid derivatives Chemical class 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 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
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- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- MARRJGBPDCCAEK-FSAOVCISSA-N methyl (1r,4ar,4bs,8as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,8a,9,10,10a-decahydrophenanthrene-1-carboxylate Chemical compound C1CC(C(C)C)=C[C@@H]2CC[C@H]3[C@@](C(=O)OC)(C)CCC[C@]3(C)[C@H]21 MARRJGBPDCCAEK-FSAOVCISSA-N 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
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- 239000003094 microcapsule Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
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- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- QTDSLDJPJJBBLE-PFONDFGASA-N octyl (z)-octadec-9-enoate Chemical compound CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC QTDSLDJPJJBBLE-PFONDFGASA-N 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- ZZSIDSMUTXFKNS-UHFFFAOYSA-N perylene red Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C(=O)C=1C2=C3C4=C(OC=5C=CC=CC=5)C=1)C(=O)C2=CC(OC=1C=CC=CC=1)=C3C(C(OC=1C=CC=CC=1)=CC1=C2C(C(N(C=3C(=CC=CC=3C(C)C)C(C)C)C1=O)=O)=C1)=C2C4=C1OC1=CC=CC=C1 ZZSIDSMUTXFKNS-UHFFFAOYSA-N 0.000 description 1
- ODFKDYBAQKFTOU-KTKRTIGZSA-N phenyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC1=CC=CC=C1 ODFKDYBAQKFTOU-KTKRTIGZSA-N 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
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- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- BPJZKLBPJBMLQG-KWRJMZDGSA-N propanoyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC(=O)CC BPJZKLBPJBMLQG-KWRJMZDGSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical class CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229940066675 ricinoleate Drugs 0.000 description 1
- 150000003329 sebacic acid derivatives Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FRKHZXHEZFADLA-UHFFFAOYSA-L strontium;octadecanoate Chemical compound [Sr+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRKHZXHEZFADLA-UHFFFAOYSA-L 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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- 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
- REPPSPNSOPYUCD-UHFFFAOYSA-N tetrabutyl benzene-1,2,4,5-tetracarboxylate Chemical compound CCCCOC(=O)C1=CC(C(=O)OCCCC)=C(C(=O)OCCCC)C=C1C(=O)OCCCC REPPSPNSOPYUCD-UHFFFAOYSA-N 0.000 description 1
- FRBIXZIRQKZWGN-UHFFFAOYSA-N tetraethyl benzene-1,2,4,5-tetracarboxylate Chemical compound CCOC(=O)C1=CC(C(=O)OCC)=C(C(=O)OCC)C=C1C(=O)OCC FRBIXZIRQKZWGN-UHFFFAOYSA-N 0.000 description 1
- GNCDUZFXTFAOBE-UHFFFAOYSA-N tetrakis(2-ethylhexyl) benzene-1,2,4,5-tetracarboxylate Chemical compound CCCCC(CC)COC(=O)C1=CC(C(=O)OCC(CC)CCCC)=C(C(=O)OCC(CC)CCCC)C=C1C(=O)OCC(CC)CCCC GNCDUZFXTFAOBE-UHFFFAOYSA-N 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- RJIFVNWOLLIBJV-UHFFFAOYSA-N tributyl benzene-1,2,4-tricarboxylate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)C(C(=O)OCCCC)=C1 RJIFVNWOLLIBJV-UHFFFAOYSA-N 0.000 description 1
- 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
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 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
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-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
- 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
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 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
- 239000012463 white pigment Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/18—Slush casting, i.e. pouring moulding material into a hollow mould with excess material being poured off
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/22—Making multilayered or multicoloured articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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Abstract
提供一種氯乙烯樹脂組成物,能夠製造得以具有優良的表面滑順性,得以於被堆疊的發泡聚胺酯成形體中抑制空隙產生的氯乙烯樹脂成形體。本發明之氯乙烯樹脂組成物包含氯乙烯樹脂、塑化劑及醚改質矽油。
Description
本發明係關於一種氯乙烯樹脂組成物、氯乙烯樹脂成形體及堆疊體。
由於氯乙烯樹脂一般具有優良的耐寒性、耐熱性、耐油性等特性,故可用於各種用途。
具體而言,例如習知在形成汽車儀表板等之汽車內裝構件方面,為使用氯乙烯樹脂成形體製成之表皮、或是將發泡聚胺酯(polyurethane)等發泡體背襯於氯乙烯樹脂成形體製成之表皮而成之堆疊體作為汽車內裝材料。而且,於構成汽車儀表板等之汽車內裝構件之表皮之氯乙烯樹脂成形體中,可冀求例如抑制成形體表面發黏之良好的表面滑順性等之各種性能。
因此近年來,人們嘗試改良氯乙烯樹脂組成物及氯乙烯樹脂成形體,其得以適用於例如汽車儀表板等之汽車內裝構件之製造。
具體而言,例如於專利文獻1(日本專利公開案第2011-173974號公報)~專利文獻2(日本專利公開案第2012-7026號公報)所報告之內容中,藉由使用調配有塑化劑及矽油之粉末成形用氯乙烯樹脂組成物形成氯乙烯樹脂成形體,而得以降低該成形體中之塑化劑之滲出性(朝向表面滲出之容易程度)及毛羽附著性(以布料擦拭表面時纖維碎屑之附著容易程度)。其中,於專利文獻1中使用甲基丙烯醯氧改質矽油作為矽油,於專利文獻2中使用羥基改質矽油(矽烷醇改質矽油)作為矽油。
然而,本案發明者反覆研究之時,明瞭使用記載於專利文獻1~2之習知氯乙烯樹脂組成物形成氯乙烯樹脂成形體,且於氯乙烯樹脂成形體背襯發泡聚胺酯成形體而製造堆疊體,如此雖改善氯乙烯樹脂成形體之表面滑順性,但於發泡聚胺酯成形體中會產生較大的孔洞(void)(空隙)。因此,已知應需要進一步改善以抑制如此之空隙產生。
是以,本發明之一目的在於提供氯乙烯樹脂成形體及能夠製造該氯乙烯樹脂成形體之氯乙烯樹脂組成物,得以具有優良的表面滑順性,且得以於被堆疊的發泡聚胺酯成形體中抑制空隙產生。此外,本發明之一目的在於提供具有發泡聚胺酯成形體及氯乙烯樹脂成形體之堆疊體,具有優良的表面滑順性,且抑制空隙產生。
本案發明者以解決上述課題為目的而進行了專心致志的研究。而且,本案發明者發現若至少使用醚改質矽油作為矽油,則能夠令氯乙烯樹脂成形體實現良好的表面滑順性,且同時能夠抑制於與該氯乙烯樹脂成形體堆疊之發泡聚胺酯成形體中產生空隙,藉以完成本發明。
亦即,此發明之一目的在於有利地解決上述課題,本發明之氯乙烯樹脂組成物之特徵在於包含氯乙烯樹脂、塑化劑及矽油,前述矽油至少包含醚改質矽油。如此一來,若氯乙烯樹脂組成物含有氯乙烯樹脂、塑化劑及指定矽油,則由該組成物成形而成之氯乙烯樹脂成形體具有優良的表面滑順性,且能夠於與發泡聚胺酯成形體堆疊時抑制該發泡聚胺酯成形體中產生空隙。
於此,本發明之氯乙烯樹脂組成物中之前述醚改質矽油之HLB值為3以下者為佳。其原因在於醚改質矽油之HLB值若為上述之上限以下,則能夠更為提升由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之表面滑順性。其結果,能夠更為良好地兼顧氯乙烯樹脂成形體之表面滑順性,以及堆疊於該氯乙烯樹脂成形體之發泡聚胺酯成形體中產生空隙之情形之抑制。
而且,本發明中之「HLB值」意指Hydrophile-Lipophile Balance,且依照格利分法(Griffin’s Method)而由以下式(3)表示,且為表示親水性程度及親油性程度之指標。
HLB值=20×(鏈狀環氧乙烷構造之式量之總和/分子量) …(3)。
於此,本發明中之「鏈狀環氧乙烷構造」為於後詳述之鏈狀的環氧乙烷(ethylene oxide)構造,且不含例如環氧基等之環狀的環氧乙烷構造。
而且,本發明之氯乙烯樹脂組成物中,前述矽油亦以更包含脂肪酸醯胺改質矽油及未改質矽油之至少一者為佳。其原因在於氯乙烯樹脂組成物若除了醚改質矽油以外更含有脂肪酸醯胺改質矽油及/或未改質矽油,則能夠更為提升由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之表面滑順性。其結果,能夠更為良好地兼顧氯乙烯樹脂成形體之表面滑順性,以及堆疊於該氯乙烯樹脂成形體之發泡聚胺酯成形體產生空隙之情形之抑制。
而且,本發明之氯乙烯樹脂組成物中,前述醚改質矽油之含有量以大於前述脂肪酸醯胺改質矽油之含有量及前述未改質矽油之含有量之總和為佳。於醚改質矽油併用脂肪酸醯胺改質矽油及/或未改質矽油之情況下,矽油中之醚改質矽油之含有量多於脂肪酸醯胺改質矽油及未改質矽油之總和含有量,則能夠良好地維持由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之表面滑順性,且同時能夠更為良好地抑制與該氯乙烯樹脂成形體堆疊之發泡聚胺酯成形體中產生空隙。
而且,本發明之氯乙烯樹脂組成物中,於醚改質矽油併用脂肪酸醯胺改質矽油及/或未改質矽油之情況下,前述醚改質矽油之HLB值為4以上者為佳。其原因在於醚改質矽油併用脂肪酸醯胺改質矽油及/或未改質矽油之情況下,若使用HLB值為上述之下限以上之醚改質矽油,則能夠維持由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之良好的表面滑順性,且同時更能夠抑制與該氯乙烯樹脂成形體堆疊之發泡聚胺酯成形體中產生空隙。
而且,本發明之氯乙烯樹脂組成物中,前述醚改質矽油之主鏈由矽氧烷鍵結而成,且前述醚改質矽油由將醚基導入至前述主鏈、前述主鏈之側鏈及前述主鏈之末端之至少一者而成,前述醚基具有以一般式(1)及一般式(2)表示之構造,且以無不飽和鍵為佳,其中:
-(C2
H4
O)x
- (1),於式(1)中之x為1以上之自然數,
-(C3
H6
O)y
- (2),於式(2)中之y為1以上之自然數。
其原因在於醚改質矽油若導入如上所述之指定醚基,則能夠更為良好地兼顧由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之表面滑順性,以及堆疊於該氯乙烯樹脂成形體之發泡聚胺酯成形體中產生空隙之情形之抑制。
而且,本發明之氯乙烯樹脂組成物中,前述醚改質矽油之動黏度為65 cSt以上者為佳。其原因在於醚改質矽油之動黏度若為上述之下限以上,則能夠良好地維持使用氯乙烯樹脂組成物而獲得之氯乙烯樹脂成形體之表面滑順性,且同時能夠更進一步抑制堆疊於該氯乙烯樹脂成形體之發泡聚胺酯成形體中之空隙之產生。
而且,本發明中之「動黏度」能夠依照ASTM D 445-46T且於溫度為攝氏25度下如同記載於實施例之方法量測。而且,使用相異二種以上之醚改質矽油混合物之情況下,「動黏度」能夠量測作為混合物整體之數值。
而且,本發明之氯乙烯樹脂組成物中,相對於前述氯乙烯樹脂為100質量份,前述塑化劑之含有量為70質量份以上者為佳。其原因在於塑化劑之含有量若為上述下限以上,則能夠使用氯乙烯樹脂組成物而良好地獲得氯乙烯樹脂成形體。
再者,本發明之氯乙烯樹脂組成物以使用於粉體成形者為佳。其原因在於若將氯乙烯樹脂組成物使用於粉體成形,則能夠更為合適地將氯乙烯樹脂組成物使用於氯乙烯樹脂成形體之形成,所述氯乙烯樹脂成形體例如利用於汽車儀表板等之汽車內裝構件。
並且,本發明之氯乙烯樹脂組成物以使用於粉末搪塑(powder slush)成形者為佳。其原因在於若將氯乙烯樹脂組成物使用於粉末搪塑成形,則能夠更為合適地將氯乙烯樹脂組成物使用於氯乙烯樹脂成形體之形成,所述氯乙烯樹脂成形體例如利用於汽車儀表板等之汽車內裝構件。
而且,此發明之一目的在於有利地解決上述課題,本發明之氯乙烯樹脂成形體之一特徵在於由上述之任一種氯乙烯組成物成形而成。若使用上述氯乙烯樹脂組成物形成氯乙烯樹脂成形體,則能夠實現良好的表面滑順性,且同時能夠良好地抑制堆疊於該氯乙烯樹脂成形體之發泡聚胺酯成形體中產生空隙。
於此,本發明之氯乙烯樹脂成形體為用於汽車儀表板表皮者為佳。其原因在於若將本發明之氯乙烯樹脂成形體使用於汽車儀表板之表皮,則得以良好地抑制表面發黏現象,且得以製造良好地背襯有發泡聚胺酯成形體之汽車儀表板。
再者,此發明之一目的在於有利地解決上述課題,本發明之堆疊體之特徵在於具有發泡聚胺酯成形體及上述之任一種氯乙烯樹脂成形體。若使用發泡聚胺酯成形體及上述氯乙烯樹脂成形體形成堆疊體,則能夠良好地堆疊發泡聚胺酯成形體及氯乙烯樹脂成形體,且同時因具有優良的表面滑順性而能夠獲得適於作為例如汽車內裝件之堆疊體。
若根據本發明,而能夠提供氯乙烯樹脂成形體及能夠製造該氯乙烯樹脂成形體之氯乙烯樹脂組成物,氯乙烯樹脂成形體具有優良的表面滑順性,且得以於被堆疊的發泡聚胺酯成形體中抑制空隙產生。
此外,若根據本發明,而能夠提供具有發泡聚胺酯成形體及氯乙烯樹脂成形體之堆疊體,其具有優良的表面滑順性,且抑制空隙產生。
以下,將詳細說明關於本發明之實施型態。
本發明之氯乙烯樹脂組成物例如能夠於欲製得本發明之氯乙烯樹脂成形體時使用。而且,由本發明之氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體,能夠例如使用於具有該氯乙烯樹脂成形體之堆疊體之製造。並且,本發明之氯乙烯樹脂成形體能夠適用於例如汽車儀表板等之汽車內裝構件之表皮等之汽車內裝件。
(氯乙烯樹脂組成物)
本發明之氯乙烯樹脂組成物之特徵在於包含氯乙烯樹脂、塑化劑及矽油,該矽油至少包含醚改質矽油。而且,本發明之氯乙烯樹脂組成物除了上述成分以外,亦可任意地更含有脂肪酸醯胺改質矽油、未改質矽油等之其他矽油、添加劑等。並且,由於本發明之氯乙烯樹脂組成物含有上述指定成分,故若使用本發明之氯乙烯樹脂組成物,則能夠獲得表面滑順性優良之氯乙烯樹脂成形體。而且,將發泡聚胺酯成形體堆疊於由本發明之氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體時,能夠抑制於該發泡聚胺酯成形體中產生空隙,而能夠良好地製造具有氯乙烯樹脂成形體及發泡聚胺酯成形體之堆疊體。
<氯乙烯樹脂>
於此,氯乙烯樹脂組成物所含有之氯乙烯樹脂能夠例如含有一種或二種以上之氯乙烯樹脂粒子,能夠任意地更含有一種或二種以上之氯乙烯樹脂微粒子。其中,氯乙烯樹脂以至少含有氯乙烯樹脂粒子為佳,以含有氯乙烯樹脂粒子及氯乙烯樹脂微粒子為較佳,以含有一種氯乙烯樹脂粒子及二種氯乙烯樹脂微粒子為更佳。
並且,於本說明書中,「樹脂粒子」意指粒子徑為30 μm以上之粒子,「樹脂微粒子」意指粒子徑未達30 μm之粒子。
而且,亦可藉由懸浮聚合法、乳化聚合法、溶液聚合法、塊狀聚合法等以往已知之任一製造法而製造氯乙烯樹脂。
<<組成>>
氯乙烯樹脂除了列舉有氯乙烯單體單元而成之均聚物以外,還列舉有氯乙烯系共聚物,所述氯乙烯系共聚物所含有之氯乙烯單體單元以50質量%以上為佳,且以70質量%以上為較佳。得以構成氯乙烯系共聚物之氯乙烯單體及能夠共聚之單體(共單體)之具體範例,列舉有乙烯(ethylene)、丙烯(propylene)等之烯烴(olefin)類;氯化烯丙基(allyl chloride)、氯化亞乙烯(vinylidene chloride)、氟乙烯(vinyl fluoride)、三氟氯乙烯(trifluorochloroethylene)等之鹵代烯烴(halogenated olefin)類;乙酸乙烯酯(vinyl acetate)、丙酸乙烯酯(vinyl propionate)等之羧酸乙烯酯(carboxylic acid vinyl ester)類;異丁基乙烯基醚(isobutyl vinyl ether)、十六烷基乙烯基醚(cetyl vinyl ether)等之乙烯基醚(vinyl ether)類;烯丙基-3-氯-2-丙氧基醚(allyl-3-chloro-2-oxypropyl ether)、烯丙基縮水甘油醚(allyl glycidyl ether)等之烯丙基醚(allyl ether)類;丙烯酸(acrylic acid)、馬來酸(maleic acid)、衣康酸(itaconic acid)、丙烯酸-2-羥乙酯(2-hydroxyethyl acrylate)、甲基丙烯酸甲酯(methyl methacrylate)、馬來酸單甲酯(monomethyl maleate)、馬來酸二乙酯(diethyl maleate)、順丁烯二酸酐(maleic anhydride)等之不飽和羧酸、其酯類或其酸酐類;丙烯腈(acrylonitrile)、甲基丙烯腈(methacrylonitrile)等之不飽和腈類;丙烯醯胺(acrylamide)、N-羥甲基丙烯醯胺(N-methylol acrylamide)、丙烯醯胺基-2-甲基丙磺酸(acrylamide-2-methylpropanesulfonic acid)、(甲基)丙烯醯胺丙基三甲基氯化銨((meth)acrylamidopropyl trimethyl ammonium chloride)等之丙烯醯胺類;丙烯胺苯甲酸鹽(allylamine benzoate salt)、二烯丙基二甲基氯化銨(diallyldimethylammonium chloride)等之烯丙基胺(allylamine)及其衍生物等。以上所例示之單體不過是共單體之一部分,共單體可使用近畿化學協會乙烯基部會編「聚氯乙烯」日刊工業新聞社(1988年)第75~104頁所例示之各種單體。此些共單體可僅使用一種,亦可使用二種以上。而且,關於上述氯乙烯樹脂,於乙烯-乙酸乙烯酯共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、氯化聚乙烯等之樹脂中,含有(1)氯乙烯或(2)氯乙烯與前述共單體所接枝聚合之樹脂。
於此,於本說明書中所謂「(甲基)丙烯酸」意謂丙烯酸及/或甲基丙烯酸。
<<氯乙烯樹脂粒子>>
氯乙烯樹脂組成物中,氯乙烯樹脂粒子通常具有基質樹脂(基材)之功能。而且,氯乙烯樹脂粒子以藉由懸浮聚合法製造者為佳。
[平均聚合度]
於此,氯乙烯樹脂粒子之平均聚合度為500以上為佳,為1000以上為較佳,為1500以上為更佳,且為5000以下為佳,為3000以下為較佳,為2500以下為更佳,以2000以下為進一步更佳。其原因在於氯乙烯樹脂粒子之平均聚合度若為上述下限以上,則能夠充分確保由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之物理強度,且能夠因於低溫下具有良好的延展性,而適合於例如利用氯乙烯樹脂成形體作為汽車儀表板表皮之情況。而且,其原因在於氯乙烯樹脂粒子之平均聚合度若為上述上限以下,則能夠提升氯乙烯樹脂組成物之溶融性而提升表面平滑性。
並且,本發明中之「平均聚合度」能夠以JIS K6720-2為基準而量測。
[平均粒子徑]
而且,氯乙烯樹脂粒子之平均粒子徑通常為30 μm以上,為50 μm以上為佳,為100 μm以上為較佳,且為500 μm以下為佳,為200 μm以下為較佳。其原因在於氯乙烯樹脂粒子之平均粒子徑若為上述下限以上,則能夠更為提升氯乙烯樹脂組成物之粉體流動性。而且,其原因在於氯乙烯樹脂粒子之平均粒子徑若為上述上限以下,則能夠更為提升氯乙烯樹脂組成物之溶融性,且同時能夠更為提升使用該組成物而形成之氯乙烯樹脂成形體之表面平滑性。
並且於本發明中,「平均粒子徑」為能夠以JIS Z8825基準且藉由雷射繞射法而量測作為體積平均粒子徑者。
[含有比例]
再者,於氯乙烯樹脂總和為100質量%中,氯乙烯樹脂中之氯乙烯樹脂粒子之含有比例以70質量%以上為佳,以80質量%以上為較佳,能夠定為100質量%,且以95質量%以下為佳,以90質量%以下為較佳。其原因在於氯乙烯樹脂中之氯乙烯樹脂粒子之含有比例若為上述下限以上,則能夠充分確保由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之物理強度,且同時能夠於低溫下具有更為良好的延展性。而且,其原因在於氯乙烯樹脂中之氯乙烯樹脂粒子之含有比例若為上述上限以下,則能夠更加提升氯乙烯樹脂組成物之粉體流動性。
<<氯乙烯樹脂微粒子>>
於氯乙烯樹脂組成物中,氯乙烯樹脂微粒子通常具有除塵劑(粉體流動性改良劑)之功能。而且,氯乙烯樹脂微粒子以藉由乳化聚合法而製造者為佳。
[平均聚合度]
於此,氯乙烯樹脂微粒子之平均聚合度以500以上為佳,以700以上為較佳,且以5000以下為佳,以3000下為較佳,以2500以下為更佳。再者,例如於併用具有相異平均聚合度之二種氯乙烯樹脂微粒子而作為除塵劑之情況下,所併用之除塵劑之平均聚合度之平均值以1000以上為佳,且以未達1500為佳。其原因在於作為除塵劑之氯乙烯樹脂微粒子之平均聚合度若為上述下限以上,則可令氯乙烯樹脂組成物具有更為良好的粉體流動性,且同時可令使用該組成物而製得之成形體於低溫下具有更為良好的延展性。而且,其原因在於氯乙烯樹脂微粒子之平均聚合度若為上述上限以下,則更為提升氯乙烯樹脂組成物之溶融性,且更為提升由該組成物而成形之氯乙烯樹脂成形體之表面平滑性。
[平均粒子徑]
而且,氯乙烯樹脂微粒子之平均粒子徑通常未達30 μm,以10 μm以下為佳,且以0.1 μm以上為佳。其原因在於氯乙烯樹脂微粒子之平均粒子徑若為上述下限以上,則不會過度縮小例如作為除塵劑之尺寸,且能夠更為良好地發揮氯乙烯樹脂組成物之粉體流動性。而且,其原因在於氯乙烯樹脂微粒子之平均粒子徑若為上述上限以下,則能夠更為提升氯乙烯樹脂組成物之溶融性,且能夠更為提升所形成之氯乙烯樹脂成形體之平滑性。
[含有比例]
再者,於氯乙烯樹脂為100質量%中,氯乙烯樹脂中之氯乙烯樹脂微粒子之含有比例以5質量%以上為佳,以10質量%以上為較佳,且以30質量%以下為佳,以20質量%以下為較佳,亦可為0質量%。其原因在於氯乙烯樹脂中之氯乙烯樹脂微粒子之含有比例若為上述下限以上,則可更加提升氯乙烯樹脂組成物之粉體流動性。而且,其原因在於氯乙烯樹脂中之氯乙烯樹脂微粒子之含有比例若為上述上限以下,則能夠更為提升由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之物理強度以及其於低溫下之延展性。
<塑化劑>
本發明之氯乙烯樹脂組成物有更包含塑化劑之必要。氯乙烯樹脂組成物若未包含塑化劑,則無法使用氯乙烯樹脂組成物而良好地獲得氯乙烯樹脂成形體。
<<含有量>>
於此,相對於上述氯乙烯樹脂100質量份,塑化劑之含有量以70質量份以上為佳,以80質量份以上為較佳,以92質量份以上為更佳,以97質量份以上為進一步更佳,且以200質量份以下為佳,以150質量份以下為較佳,以100質量份以下為更佳。其原因在於塑化劑之含有量若為上述下限以上,則可對於氯乙烯樹脂組成物賦予優良的柔軟性,而能夠易於例如對氯乙烯樹脂成形體加工,且同時能夠對所得到之氯乙烯樹脂成形體賦予低溫下之良好的延展性。而且,其原因在於塑化劑之含有量若為上述上限以下,則能夠更為抑制所得到之氯乙烯樹脂成形體之表面發黏,且能夠更為提升表面滑順性。
<<種類>>
於此,列舉以下之一次塑化劑及二次塑化劑等作為塑化劑之具體範例。
所謂的一次塑化劑列舉有偏苯三酸三甲基酯(trimethyl trimellitate)、偏苯三酸三乙基酯(triethyl trimellitate)、偏苯三酸三正丙基酯(tri-n-propyl trimellitate)、偏苯三酸三正丁基酯(tri-n-butyl trimellitate)、偏苯三酸三正戊基酯(tri-n-pentyl trimellitate)、偏苯三酸三正己基酯(tri-n-hexyl trimellitate)、偏苯三酸三正庚基酯(tri-n-heptyl trimellitate)、偏苯三酸三正辛基酯(tri-n-octyl trimellitate)、偏苯三酸三正壬基酯(tri-n-nonyl trimellitate)、偏苯三酸三正癸基酯(tri-n-decyl trimellitate)、偏苯三酸三正十一烷基酯(tri-n-undecyl trimellitate)、偏苯三酸三正十二烷基酯(tri-n-dodecyl trimellitate)、偏苯三酸三正十三烷基酯(tri-n-tridecyl trimellitate)、偏苯三酸三正十四烷基酯(tri-n-tetradecyl trimellitate)、偏苯三酸三正十五烷基酯(tri-n-pentadecyl trimellitate)、偏苯三酸三正十六烷基酯(tri-n-hexadecyl trimellitate)、偏苯三酸三正十七烷基酯(tri-n-heptadecyl trimellitate)、偏苯三酸三正十八烷基酯(tri-n-stearyl trimellitate)、偏苯三酸三正烷基酯(於此,偏苯三酸三正烷基酯所具有之烷基之碳原子數於單一分子中亦可彼此相異)等構成酯之烷基為直鏈狀之直鏈狀偏苯三酸酯[其中,此些偏苯三酸酯可由單一化合物而成,亦可為混合物];
偏苯三酸三異丙基酯(tri-i-propyl trimellitate)、偏苯三酸三異丁基酯(tri-i-butyl trimellitate)、偏苯三酸三異戊基酯(tri-i-pentyl trimellitate)、偏苯三酸三異己基酯(tri-i-hexyl trimellitate)、偏苯三酸三異庚基酯(tri-i-heptyl trimellitate)、偏苯三酸三異辛基酯(tri-i-octyl trimellitate)、偏苯三酸三(2-乙基己基)酯(tri-(2-ethylhexyl) trimellitate)、偏苯三酸三異壬基酯(tri-i-nonyl trimellitate)、偏苯三酸三異癸基酯(tri-i-decyl trimellitate)、偏苯三酸三異十一基酯(tri-i-undecyl trimellitate)、偏苯三酸三異十二基酯(tri-i-dodecyl trimellitate)、偏苯三酸三異十三基酯(tri-i-tridecyl trimellitate)、偏苯三酸三異十四基酯(tri-i-tetradecyl trimellitate)、偏苯三酸三異十五基酯(tri-i-pentadecyl trimellitate)、偏苯三酸三異十六基酯(tri-i-hexadecyl trimellitate)、偏苯三酸三異十七基酯(tri-i-heptadecyl trimellitate)、偏苯三酸三異十八基酯(tri-i-octadecyl trimellitate)、偏苯三酸三烷基酯(於此,偏苯三酸三烷基酯所具有之烷基之碳原子數於單一分子中亦可彼此相異)等構成酯之烷基為分支狀之分支狀偏苯三酸酯[其中,此些偏苯三酸酯可由單一化合物而成,亦可為混合物];
均苯四酸四甲基酯(tetramethyl pyromellitate)、均苯四酸四乙基酯(tetraethyl pyromellitate)、均苯四酸四正丙基酯(tetra-n-propyl pyromellitate)、均苯四酸四正丁基酯(tetra-n-butyl pyromellitate)、均苯四酸四正戊基酯(tetra-n-pentyl pyromellitate)、均苯四酸四正己基酯(tetra-n-hexyl pyromellitate)、均苯四酸四正庚基酯(tetra-n-heptyl pyromellitate)、均苯四酸四正辛基酯(tetra-n-octyl pyromellitate)、均苯四酸四正壬基酯(tetra-n-nonyl pyromellitate)、均苯四酸四正癸基酯(tetra-n-decyl pyromellitate)、均苯四酸四正十一烷基酯(tetra-n-undecyl pyromellitate)、均苯四酸四正十二烷基酯(tetra-n-dodecyl pyromellitate)、均苯四酸四正十三烷基酯(tetra-n-tridecyl pyromellitate)、均苯四酸四正十四烷基酯(tetra-n-tetradecyl pyromellitate)、均苯四酸四正十五烷基酯(tetra-n-pentadecyl pyromellitate)、均苯四酸四正十六烷基酯(tetra-n-hexadecyl pyromellitate)、均苯四酸四正十七烷基酯(tetra-n-heptadecyl pyromellitate)、均苯四酸四正十八烷基酯(tetra-n-stearyl pyromellitate)、均苯四酸四正烷基酯(於此,均苯四酸四正烷基酯所具有之烷基之碳原子數於單一分子中亦可彼此相異)等構成酯之烷基為直鏈狀之直鏈狀均苯四酸酯[其中,此些均苯四酸酯可由單一化合物而成,亦可為混合物];
均苯四酸四異丙基酯(tetra-i-propyl pyromellitate)、均苯四酸四異丁基酯(tetra-i-butyl pyromellitate)、均苯四酸四異戊基酯(tetra-i-pentyl pyromellitate)、均苯四酸四異己基酯(tetra-i-hexyl pyromellitate)、均苯四酸四異庚基酯(tetra-i-heptyl pyromellitate)、均苯四酸四異辛基酯(tetra-i-octyl pyromellitate)、均苯四酸四(2-乙基己基)酯(tetra-(2-ethylhexyl) pyromellitate)、均苯四酸四異壬基酯(tetra-i-nonyl pyromellitate)、均苯四酸四異癸基酯(tetra-i-decyl pyromellitate)、均苯四酸四異十一基酯(tetra-i-undecyl pyromellitate)、均苯四酸四異十二基酯(tetra-i-dodecyl pyromellitate)、均苯四酸四異十三基酯(tetra-i-tridecyl pyromellitate)、均苯四酸四異十四基酯(tetra-i-tetradecyl pyromellitate)、均苯四酸四異十五基酯(tetra-i-pentadecyl pyromellitate)、均苯四酸四異十六基酯(tetra-i-hexadecyl pyromellitate)、均苯四酸四異十七基酯(tetra-i-heptadecyl pyromellitate)、均苯四酸四異十八基酯(tetra-i-octadecyl pyromellitate)、均苯四酸四烷基酯(於此,均苯四酸四烷基酯所具有之烷基之碳原子數於單一分子中亦可彼此相異)等構成酯之烷基為分支狀之分支狀均苯四酸酯[其中,此些均苯四酸酯可由單一化合物而成,亦可為混合物];
鄰苯二甲酸二甲基酯(dimethyl phthalate)、鄰苯二甲酸二乙基酯(diethyl phthalate)、鄰苯二甲酸二丁基酯(dibutyl phthalate)、鄰苯二甲酸二(2-乙基己基)酯(di-(2-ethylhexyl) phthalate)、鄰苯二甲酸二正辛基酯(di-n-octyl phthalate)、鄰苯二甲酸二異丁基酯(diisobutyl phthalate)、鄰苯二甲酸二庚基酯(diheptyl phthalate)、鄰苯二甲酸二苯基酯(diphenyl phthalate)、鄰苯二甲酸二異癸基酯(diisodecyl phthalate)、鄰苯二甲酸二-十三烷基酯(ditridecyl phthalate)、鄰苯二甲酸二-十一烷基酯(diundecyl phthalate)、鄰苯二甲酸二芐基酯(dibenzyl phthalate)、鄰苯二甲酸丁基芐基酯(butyl benzyl phthalate)、鄰苯二甲酸二壬基酯(dinonyl phthalate)、鄰苯二甲酸二環己基酯(dicyclohexyl phthalate)等之鄰苯二甲酸衍生物;
間苯二甲酸二甲基酯(dimethyl isophthalate)、間苯二甲酸二(2-乙基己基)酯(di-(2-ethylhexyl) isophthalate)、間苯二甲酸二異辛基酯(diisooctyl isophthalate)等之間苯二甲酸衍生物;
四氫鄰苯二甲酸二(2-乙基己基)酯(di-(2-ethylhexyl) tetrahydrophthalate)、四氫鄰苯二甲酸二正辛基酯(di-n-octyl tetrahydrophthalate)、四氫鄰苯二甲酸二異癸基酯diisodecyl tetrahydrophthalate)等之四氫鄰苯二甲酸衍生物;
己二酸二正丁基酯(di-n-butyl adipate)、己二酸二(2-乙基己基)酯(di-(2-ethylhexyl) adipate)、己二酸二異癸基酯(diisodecyl adipate)、己二酸二異壬基酯(diisononyl adipate)等之己二酸衍生物;
壬二酸二(2-乙基己基)酯(di-(2-ethylhexyl) azelate)、壬二酸二異辛基酯(diisooctyl azelate)、壬二酸二正己基酯(di-n-hexyl azelate)等之壬二酸衍生物;
癸二酸二正丁基酯(di-n-butyl sebacate)、癸二酸二(2-乙基己基)酯(di-(2-ethylhexyl) sebacate)、癸二酸二異癸基酯diisodecyl sebacate)、癸二酸二(2-丁基辛基)酯(di-(2-butyloctyl) sebacate)等之癸二酸衍生物;
馬來酸二正丁基酯(di-n-butyl maleate)、馬來酸二甲基酯(dimethyl maleate)、馬來酸二乙基酯(diethyl maleate)、二馬來酸二(2-乙基己基)酯(di-(2-ethylhexyl) maleate)等之馬來酸衍生物;
富馬酸二正丁基酯(di-n-butyl fumarate)、富馬酸二(2-乙基己基)酯(di-(2-ethylhexyl) fumarate)等之富馬酸衍生物;
檸檬酸三乙基酯(triethyl citrate)、檸檬酸三正丁基酯(tri-n-butyl citrate)、檸檬酸乙醯基三乙基酯(acetyl triethyl citrate)、檸檬酸乙醯基三(2-乙基己基)酯(acetyl tri- (2-ethylhexyl) citrate)等之檸檬酸衍生物;
衣康酸單甲基酯(monomethyl itaconate)、衣康酸單丁基酯(monobutyl itaconate)、衣康酸二甲基酯(dimethyl itaconate)、衣康酸二乙基酯(diethyl itaconate)、衣康酸二丁基酯(dibutyl itaconate)、衣康酸二(2-乙基己基)酯(di-(2-ethylhexyl) itaconate)等之衣康酸衍生物;
油酸丁基酯(butyl oleate)、單油酸甘油基酯(glyceryl monooleate)、單油酸二乙二醇酯(diethylene glycol monooleate)等之油酸衍生物;
乙醯蓖麻油酸甲基酯(methyl acetyl ricinoleate)、乙醯蓖麻油酸丁基酯(butyl acetyl ricinoleate)、單蓖麻油酸甘油基酯(glyceryl monoricinolate)、單蓖麻油酸二乙二醇酯(diethylene glycol monoricinolate)等之蓖麻油酸衍生物;
硬脂酸正丁基酯(n-butyl stearate)、二硬脂酸二乙二醇酯(diethylene glycol distearate)等之硬脂酸衍生物(惟排除12-羥基硬脂酸及其酯);
單月桂酸二乙二醇酯(diethylene glycol monolaurate)、二壬酸二乙二醇酯(diethylene glycol dipelargonate)、季戊四醇脂肪酸酯等之其他脂肪酸衍生物;
磷酸三乙基酯(triethyl phosphate)、磷酸三丁基酯(tributyl phosphate)、磷酸三(2-乙基己基)酯(tri-(2-ethylhexyl) phosphate)、磷酸三丁氧基乙基酯(tributoxyethyl phosphate)、磷酸三苯基酯(triphenyl phosphate)、磷酸甲苯酚基二苯基酯(cresyl diphenyl phosphate)、磷酸三甲苯酚基酯(tricresyl phosphate)、磷酸三-二甲苯基酯(trixylenyl phosphate)、磷酸三(氯乙基)酯(tris (chloroethyl) phosphate)等之磷酸衍生物;
二苯甲酸二乙二醇酯(diethylene glycol dibenzoate)、二苯甲酸二丙二醇酯(dipropylene glycol dibenzoate)、二苯甲酸三乙二醇酯(triethylene glycol dibenzoate)、二(2-乙基丁酸)三乙二醇酯(triethylene glycol di-(2-ethyl butyrate))、二(2-乙基己酸)三乙二醇酯(triethylene glycol di-(2-ethyl hexoate))、亞甲基雙巰乙酸二丁基酯(dibutyl methylene bisthioglycolate)等之乙二醇衍生物;
單乙酸甘油基酯(glycerol monoacetate)、三醋酸甘油基酯(glycerol triacetate)、三丁酸甘油基酯(glycerol tributyrate)等之甘油衍生物;
環氧六氫鄰苯二甲酸二異癸基酯(diisodecyl epoxyhexahydrophthalate)、環氧三酸甘油酯(epoxy triglyceride)、環氧化油酸辛基酯(epoxidized octyl oleate)、環氧化油酸癸基酯(epoxidized decyl oleate)等之環氧衍生物;
己二酸系聚酯、癸二酸系聚酯、鄰苯二甲酸系聚酯等之聚酯系塑化劑等。
另外,所謂的二次塑化劑列舉有環氧化大豆油、環氧化亞麻仁油等之環氧化植物油;氯化石蠟、二辛酸三乙二醇酯(triethylene glycol dicaprylate)等之乙二醇之脂肪酸酯、環氧硬脂酸丁基酯(butyl epoxy stearate)、油酸苯基酯(phenyl oleate)、二氫松脂酸甲基酯(methyl dihydroabietate)等。
而且,此些塑化劑可僅使用一種,亦可例如併用一次塑化劑、二次塑化劑等之二種以上。其中,於使用二次塑化劑之情況下,以併用與該二次塑化劑同等質量以上之一次塑化劑者為佳。
再者,於上述塑化劑中,由令氯乙烯樹脂組成物之成形性更為良好之觀點看來,以使用偏苯三酸酯及/或均苯四酸酯者為佳,以使用偏苯三酸酯為較佳,以使用直鏈狀偏苯三酸酯為更佳,以使用分子內具有二個以上碳原子數相異之烷基之直鏈狀偏苯三酸酯為進一步更佳。而且,該烷基之碳原子數以8~10者為佳,該烷基以正辛基、正癸基為較佳。再者,更以使用上述偏苯三酸酯以及環氧化大豆油為佳。
<矽油>
本發明之氯乙烯樹脂組成物所含有之矽油其特徵在於至少含有醚改質矽油。一般而言,塑化劑易於成為成形體之表面發黏之原因,此時藉由氯乙烯樹脂組成物含有醚改質矽油,而即使為由含有塑化劑之氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體,亦可具有良好的表面滑順性,且能夠良好地抑制於與該氯乙烯樹脂成形體堆疊之發泡聚胺酯成形體中產生空隙。
而且,本發明之氯乙烯樹脂組成物所含有之矽油除了醚改質矽油以外,亦以更包含脂肪酸醯胺改質矽油及未改質矽油之至少一者為佳。具體而言,本發明之氯乙烯樹脂組成物亦可僅含有醚改質矽油,亦以含有醚改質矽油及脂肪酸醯胺改質矽油為佳,亦以含有醚改質矽油及未改質矽油為佳,亦以含有醚改質矽油、脂肪酸醯胺改質矽油及未改質矽油為佳。此外,本發明之氯乙烯樹脂組成物除了上述各種矽油以外,亦可更包含任意的其他矽油。
並且,因含有醚改質矽油而兼顧上述表面滑順性之提升及空隙產生之抑制,於塑化劑之含有量較多之情況下,具體為相對於氯乙烯樹脂100質量份而塑化劑之含有量為70質量份以上之情況下,可實現更進一步之效果。
而且,於本發明中,醚改質矽油、脂肪酸醯胺改質矽油及未改質矽油等之「矽油」並未特別限定,通常於常溫常壓下能夠具有流動性,例如為液體狀;膠狀等半固體狀。
於此,本發明中之所謂「常溫」指的是攝氏23度,所謂「常壓」指的是1大氣壓(絕對壓力)。
<<醚改質矽油>>
於此,醚改質矽油通常為將醚基導入至由矽氧烷鍵結(-Si-O-Si-)而成之主鏈、上述主鏈之側鏈及上述主鏈之末端之至少一者而成。於此,將醚基導入至上述主鏈之情況中,醚基鍵結於上述主鏈之途中。此外,將醚基導入至上述末端之情況中,可導入至其中一末端,亦可導入至二末端。而且,醚改質矽油亦可為將醚基以外之其他置換基更導入至上述主鏈、上述主鏈之側鏈及/或上述主鏈之末端而成。
此外,醚改質矽油以將醚基至少導入至側鏈者為佳。
[醚基]
醚基可例如列舉為具有單個或多個鏈狀環氧烷烴(alkylene oxide)構造之置換基。具體而言,醚基例如列舉為僅具有以下述一般式(1):-(C2
H4
O)x
- (1)[於式(1)中之x為1以上之自然數]表示之鏈狀環氧乙烷構造(式(1)中x為2以上之自然數之情況下稱之為「聚環氧乙烷基」)之置換基;具有上述鏈狀環氧乙烷構造及任意比例之以下述一般式(2):-(C3
H6
O)y
- (2)[於式(2)中之y為1以上之自然數]表示之鏈狀環氧丙烷(propylene oxide)構造(式(2)中y為2以上之自然數之情況下稱之為「聚環氧丙烷基」)之置換基;除了上述鏈狀環氧乙烷構造以外更具有鏈狀環氧烷烴構造以外之任意有機構造(以下以「R」、「R’」表示)之置換基(例如-R-(C2
H4
O)x
-R’);除了上述鏈狀環氧乙烷構造及鏈狀環氧丙烷構造等之鏈狀環氧烷烴構造以外更具有上述任意有機構造R、R’之置換基(例如-R-(C2
H4
O)x
(C3
H6
O)y
-R’)等。於此舉例而言,亦可僅存在上述-R-(C2
H4
O)x
-R’及-R-(C2
H4
O)x
(C3
H6
O)y
-R’中之任意有機構造R及R’之其中一者。
其中,由提升氯乙烯樹脂成形體之表面滑順性且更為抑制與氯乙烯樹脂成形體堆疊之發泡聚胺酯成形體中產生空隙之觀點看來,理由雖未清楚,但醚基以至少具有鏈狀環氧乙烷構造者為佳,以具有鏈狀環氧乙烷構造及鏈狀環氧丙烷構造為較佳,以複數具有鏈狀環氧乙烷構造及鏈狀環氧丙烷構造為更佳。再者,由優化耐熱老化性之觀點看來,醚基以無不飽和鍵為進一步更佳。
[其他置換基]
得以進一步導入至醚改質矽油之其他置換基並未特別限定,例如列舉有烷基(-Ca
H2a+1
;其中a為任意之自然數)、芳烷基(例如-CH2
-CH(CH3
)-C6
H5
;其中C6
H5
為苯基)等。
[HLB値]
醚改質矽油於未併用詳述於後之脂肪酸醯胺改質矽油及/或未改質矽油之情況下,以HLB值為3以下者為佳,以HLB值為2.5以下者為較佳,以HLB值為2.2以下者為更佳,且以HLB值為1以上者為佳,以HLB值為1.5以上者為較佳,以HLB值為1.8以上者為更佳。其原因在於未併用脂肪酸醯胺改質矽油及/或未改質矽油之情況下,醚改質矽油之HLB值若為上述下限以上,則醚改質矽油得以發揮極性,而得以更為抑制發泡聚胺酯成形體於堆疊過程中產生空隙。而且,其原因在於未併用脂肪酸醯胺改質矽油及/或未改質矽油之情況下,醚改質矽油之HLB值若為上述上限以下,則醚改質矽油不會具有過度的極性,而可發揮良好的表面滑順性。並且,其原因在於未併用脂肪酸醯胺改質矽油及/或未改質矽油之情況下,醚改質矽油之HLB值若於上述範圍內,則得以更為高等級地兼顧由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之良好的表面滑順性,以及發泡聚胺酯成形體中產生空隙之情形之抑制。
而且,醚改質矽油於併用詳述於後之脂肪酸醯胺改質矽油及/或未改質矽油之情況下,以HLB值為4以上者為佳,以HLB值為5以上者為較佳,以HLB值為5.8以上者為更佳,且以HLB值為10以下者為佳,以HLB值為8以下者為較佳,以HLB值為6.2以下者為更佳。其原因在於併用脂肪酸醯胺改質矽油及/或未改質矽油之情況下,醚改質矽油之HLB值若為上述下限以上,則醚改質矽油可發揮較高的極性。而且,得以更為抑制發泡聚胺酯成形體於與氯乙烯樹脂成形體堆疊之堆疊過程中產生空隙,其中氯乙烯樹脂成形體由氯乙烯樹脂組成物成形而成。此外,一般於使用HLB值為4以上之醚改質矽油之情況下,氯乙烯樹脂成形體之表面滑順性會容易降低。然而,藉由併用詳述於後之脂肪酸醯胺改質矽油及/或未改質矽油,而能夠實現更為良好的表面滑順性。而且,其原因在於併用脂肪酸醯胺改質矽油及/或未改質矽油之情況下,醚改質矽油之HLB值若為上述上限以下,則醚改質矽油不會具有過度的極性,而得以發揮更為良好的表面滑順性。
於此,HLB值為能夠由上述之式(3)表示之指標。
[動黏度]
而且,於攝氏25度之溫度時,醚改質矽油之動黏度為65 cSt以上者為佳,為68 cSt以上者為較佳,且為4000 cSt以下者為佳,為3000 cSt以下者為較佳,為2000 cSt以下者為更佳,為1500 cSt以下者為進一步更佳。其原因在於醚改質矽油之動黏度若為上述下限以上,則消泡效果會下降,得以更為良好地保持由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之表面滑順性,且同時得以更為抑制發泡聚胺酯成形體於堆疊過程中產生空隙。而且,其原因在於醚改質矽油之動黏度若為上述上限以下,則可優化醚改質矽油之處理性。
此外,於未併用脂肪酸醯胺改質矽油及/或未改質矽油之情況下,醚改質矽油之動黏度為700 cSt以下者為特佳。其原因在於未併用脂肪酸醯胺改質矽油及/或未改質矽油之情況下,醚改質矽油之動黏度若為上述上限以下,則得以更為提升由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之表面滑順性。
[醚改質矽油之含有量]
相對於氯乙烯樹脂100質量份,醚改質矽油之含有量以0.01質量份以上為佳,以0.1質量份以上為較佳,以0.15質量份以上為更佳,且以1.5質量份以下為佳,以1.0質量份以下為較佳,以0.5質量份以下為更佳,以0.4質量份以下為進一步更佳。其原因在於醚改質矽油之含有量若為上述下限以上,則於能夠充分降低氯乙烯樹脂成形體之表面發黏的現象而具有更為優良的表面滑順性的同時,還得以更為抑制堆疊的發泡聚胺酯成形體中之空隙。而且,其原因在於醚改質矽油之含有量若為上述上限以下,則即使為例如於氯乙烯樹脂成形體連續成形之情況下,亦得以抑制因過量醚改質矽油而汙染成形用模具等之表面之情形。
相對於塑化劑100質量份,醚改質矽油之含有量以0.01質量份以上為佳,以0.1質量份以上為較佳,以0.15質量份以上為更佳,且以1.5質量份以下為佳,以1.0質量份以下為較佳,以0.5質量份以下為更佳,以0.4質量份以下為進一步更佳。其原因在於塑化劑一般易於成為成形體之表面發黏之原因,此時醚改質矽油之含有量若為上述下限以上,則於能夠充分降低氯乙烯樹脂成形體之表面發黏的現象而具有更為優良的表面滑順性的同時,還得以更為抑制堆疊的發泡聚胺酯成形體中之空隙。而且,其原因在於醚改質矽油之含有量若為上述上限以下,則即使為例如於氯乙烯樹脂成形體連續成形之情況下,亦得以抑制因過量醚改質矽油而汙染成形用模具等之表面之情形。
再者,於併用詳述於後之脂肪酸醯胺改質矽油及/或未改質矽油之情況中,矽油中之醚改質矽油之含有量以大於脂肪酸醯胺改質矽油之含有量及未改質矽油之含有量之總和者為佳。而且,於併用脂肪酸醯胺改質矽油及/或未改質矽油之情況中,醚改質矽油之含有量以脂肪酸醯胺改質矽油及未改質矽油之總和含有量之1.3倍以上者為佳,以1.6倍以上者為較佳,以5倍以下者為佳,以3倍以下者為較佳。其原因在於醚改質矽油之含有量若為上述下限以上,則得以更為抑制被堆疊的發泡聚胺酯成形體中之空隙產生。而且,其原因在於醚改質矽油之含有量若為上述上限以下,則由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體得以具有更為良好的表面滑順性。
<<脂肪酸醯胺改質矽油>>
本發明之氯乙烯樹脂組成物中,矽油得以更包含上述醚改質矽油以及脂肪酸醯胺改質矽油,其中所述脂肪酸醯胺改質矽油通常導入有以一般式(4):-NHCO-R’’ (4)[於式(4)中,R’’為烴基]表示之脂肪酸醯胺基。而且,脂肪酸醯胺改質矽油以導入有以一般式(5):-R’’’-NHCO-R’’ (5)[於式(5)中,R’’及R’’’為相同或相異的烴基]表示之脂肪酸醯胺基者為佳。若併用上述醚改質矽油及脂肪酸醯胺改質矽油而作為矽油,得以更高等級地兼顧由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之表面滑順性,以及被堆疊的發泡聚胺酯成形體中之空隙產生之抑制。
於此,脂肪酸醯胺改質矽油於上述式(4)及(5)中之R’’及R’’’之至少一者所具有之碳原子數以5以上為佳,以12以上為較佳,且碳原子數以24以下為佳,以18以下為較佳。更甚者,R’’所具有之碳原子數以12以上為更佳,以18以下為更佳。換言之,脂肪酸醯胺改質矽油為高級脂肪酸醯胺改質矽油為較佳。其原因在於若為上述構造,相對於具有較高極性之上述醚改質矽油,被併用的脂肪酸醯胺改質矽油之極性較低。並且,能夠充分抑制於被堆疊的發泡聚胺酯成形體中產生空隙,且同時能夠更加提升由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之表面滑順性。
[脂肪酸醯胺改質矽油之含有量]
而且,相對於氯乙烯樹脂為100質量份,脂肪酸醯胺改質矽油之含有量為0.005質量份以上者為佳,為0.01質量份以上者為較佳,為0.05質量份以上者為更佳,且為1.0質量份以下者為佳,為0.3質量份以下者為較佳,為0.15質量份以下者為更佳。其原因在於若以上述下限以上之含有量併用脂肪酸醯胺改質矽油,則得以充分抑制被堆疊的發泡聚胺酯成形體中之空隙,且同時得以更加降低氯乙烯樹脂成形體之表面發黏現象。而且,其原因在於若以上述上限以下之含有量併用脂肪酸醯胺改質矽油,則得以更加抑制被堆疊的發泡聚胺酯成形體中之空隙。
而且,相對於塑化劑為100質量份,脂肪酸醯胺改質矽油之含有量為0.005質量份以上者為佳,為0.01質量份以上者為較佳,為0.05質量份以上者為更佳,且為1.0質量份以下者為佳,為0.3質量份以下者為較佳,為0.15質量份以下者為更佳。其原因在於若以上述下限以上之含有量併用脂肪酸醯胺改質矽油,則得以充分抑制被堆疊的發泡聚胺酯成形體中之空隙,且同時得以更加降低氯乙烯樹脂成形體之表面發黏現象。而且,其原因在於若以上述上限以下之含有量併用脂肪酸醯胺改質矽油,則得以更加抑制被堆疊的發泡聚胺酯成形體中之空隙。
<<未改質矽油>>
本發明之氯乙烯樹脂組成物中,矽油得以更包含上述醚改質矽油以及未改質矽油。於此,未改質矽油為僅由矽氧烷鍵結(-Si-O-Si-)而成之主鏈構成之矽油,且於上述氧原子(O)以外,於該主鏈之矽原子(Si)通常鍵結有甲基(-CH3
)及/或乙基(-C2
H5
)。而且,未改質矽油於上述主鏈之矽原子僅鍵結氧原子及甲基,且於上述主鏈之側鏈及末端之任一者,以未導入上述甲基及乙基以外之置換基者為佳,且以聚二甲基矽氧烷(polydimethyl siloxane)作為未改質矽油為特佳。
[動黏度]
而且,於攝氏25度之溫度時,未改質矽油之動黏度為3000 cSt以上者為佳,為4000 cSt以上者為較佳,且為1000000 cSt以下者為佳,為500000 cSt以下者為較佳,為8000 cSt以下者為更佳。其原因在於若併用動黏度為上述下限以上之未改質矽油,則得以更為良好地兼顧氯乙烯樹脂成形體之表面滑順性,以及被堆疊的發泡聚胺酯成形體中產生空隙之抑制。而且,其原因在於未改質矽油之動黏度若為上述上限以下,則可優化未改質矽油之處理性。
[未改質矽油之含有量]
而且,相對於氯乙烯樹脂100質量份,未改質矽油之含有量以0.005質量份以上為佳,以0.01質量份以上為較佳,以0.05質量份以上為更佳,且以1.0質量份以下為佳,以0.3質量份以下為較佳,以0.15質量份以下為更佳。其原因在於若以上述下限以上之含有量併用未改質矽油,則得以充分抑制被堆疊的發泡聚胺酯成形體中之空隙,且同時得以更加降低氯乙烯樹脂成形體之表面發黏的現象。而且,其原因在於若以上述上限以下之含有量併用未改質矽油,則得以更加抑制被堆疊的發泡聚胺酯成形體中之空隙。
而且,相對於塑化劑100質量份,未改質矽油之含有量以0.005質量份以上為佳,以0.01質量份以上為較佳,以0.05質量份以上為更佳,且以1.0質量份以下為佳,以0.3質量份以下為較佳,以0.15質量份以下為更佳。其原因在於若以上述下限以上之含有量併用未改質矽油,則得以充分抑制被堆疊的發泡聚胺酯成形體中之空隙,且同時得以更加降低氯乙烯樹脂成形體之表面發黏的現象。而且,其原因在於若以上述上限以下之含有量併用未改質矽油,則得以更加抑制被堆疊的發泡聚胺酯成形體中之空隙。
[脂肪酸醯胺改質矽油及未改質矽油之總和含有量]
再者,於併用上述肪酸醯胺改質矽油及未改質矽油二者之情況下,相對於氯乙烯樹脂100質量份,脂肪酸醯胺改質矽油及未改質矽油之總和含有量以0.01質量份以上為佳,以0.03質量份以上為較佳,以0.06質量份以上為更佳,且以1.0質量份以下為佳,以0.3質量份以下為較佳,以0.15質量份以下為更佳。其原因在於若以上述下限以上之總和含有量併用脂肪酸醯胺改質矽油及未改質矽油,則得以更加降低氯乙烯樹脂成形體之表面發黏的現象。而且,其原因在於若以上述上限以下之總和含有量併用脂肪酸醯胺改質矽油及未改質矽油,則得以更加抑制被堆疊的發泡聚胺酯成形體中之空隙。
而且,相對於塑化劑100質量份,脂肪酸醯胺改質矽油及未改質矽油之總和含有量以0.01質量份以上為佳,以0.03質量份以上為較佳,以0.06質量份以上為更佳,且以1.0質量份以下為佳,以0.3質量份以下為較佳,以0.15質量份以下為更佳。其原因在於若以上述下限以上之總和含有量併用脂肪酸醯胺改質矽油及未改質矽油,則得以更加降低氯乙烯樹脂成形體之表面發黏的現象。而且,其原因在於若以上述上限以下之總和含有量併用脂肪酸醯胺改質矽油及未改質矽油,則得以更加抑制被堆疊的發泡聚胺酯成形體中之空隙。
<<矽油整體之含有量>>
並且,相對於氯乙烯樹脂100質量份, 矽油整體之含有量以0.01質量份以上為佳,以0.1質量份以上為較佳,且以1質量份以下為佳,以0.5質量份以下為較佳,以0.4質量份以下為更佳。其原因在於矽油整體之含有量若為上述下限以上,則於能夠充分降低氯乙烯樹脂成形體之表面發黏的現象而具有更加優良的表面滑順性的同時,還能夠充分抑制堆疊的發泡聚胺酯成形體中之空隙。而且,其原因在於矽油整體之含有量若為上述上限以下,則即使為例如於氯乙烯樹脂成形體連續成形之情況下,亦得以抑制因過量矽油而汙染成形用模具等之表面之情形。
而且,相對於塑化劑100質量份,矽油整體之含有量以0.01質量份以上為佳,以0.1質量份以上為較佳,且以1質量份以下為佳,以0.5質量份以下為較佳,以0.4質量份以下為更佳。其原因在於塑化劑一般易於成為成形體之表面發黏之原因,此時矽油整體之含有量若為上述下限以上,則於能夠充分降低氯乙烯樹脂成形體之表面發黏的現象而具有更加優良的表面滑順性的同時,還能夠充分抑制被堆疊的發泡聚胺酯成形體中之空隙。而且,其原因在於矽油整體之含有量若為上述上限以下,則即使為例如於氯乙烯樹脂成形體連續成形之情況下,亦得以抑制因過量矽油而汙染成形用模具等之表面之情形。
<添加劑>
本發明之氯乙烯樹脂組成物除了上述成分以外,亦可更含有各種添加劑。添加劑並未特別限定,可列舉有過氯酸處理之水滑石(hydrotalcite)、沸石(zeolite)、β-二酮(β-diketone)、脂肪酸金屬鹽等之穩定劑;離型劑;上述氯乙烯樹脂微粒子以外之除塵劑;以及其他添加劑等。
<<過氯酸處理之水滑石>>
氯乙烯樹脂組成物得以含有之過氯酸處理之水滑石,能夠藉由以下步驟而易於製造過氯酸導入型之水滑石。藉由將水滑石加入過氯酸之稀薄水溶液中攪拌,且之後依據需求進行過濾、脫水或乾燥,而以過氯酸根陰離子(Cl4 -
)置換水滑石中之碳酸根陰離子(CO3 2-
)之至少一部分(每1莫耳碳酸根陰離子以2莫耳過氯酸根陰離子置換)。上述水滑石與上述過氯酸之莫耳比雖能夠任意設定,但一般相對於水滑石1莫耳,過氯酸為0.1莫耳以上且為2莫耳以下為佳。
於此,未處理(未導入過氯酸根陰離子而未置換)之水滑石中之碳酸根陰離子之對於過氯酸根陰離子之置換率以50莫耳%以上為佳,以70莫耳%以上為較佳,以85莫耳%以上為更佳。而且,未處理(未導入過氯酸根陰離子而未置換)之水滑石中之碳酸根陰離子之對於過氯酸根陰離子之置換率以95莫耳%以下為佳。其原因在於藉由未處理(未導入過氯酸根陰離子而未置換)之水滑石中之碳酸根陰離子之對於過氯酸根陰離子之置換率為上述之範圍內,而能夠更為易於製造氯乙烯樹脂成形體。
並且,水滑石為具有層狀結晶構造之無機物質,其中層狀結晶構造為於以一般式:[Mg1-x
Alx
(OH)2
]x +
[(CO3
)x/2
‧mH2
O]x-
表示之不定比化合物中,由帶正電荷之基本層[Mg1-x
Alx
(OH)2
]x +
及帶負電荷之中間層[(CO3
)x/2
‧mH2
O]x-
而成。於此之上述一般式中,x為大於0且為0.33以下之範圍之數值。天然的水滑石為Mg6
Al2
(OH)16
CO3
‧4H2
O。合成的水滑石市售有Mg4.5
Al2
(OH)13
CO3
‧3.5H2
O。合成的水滑石之合成方法例如記載於日本專利公開案第S61-174270號公報。
於此,過氯酸處理之水滑石之含有量並未特別限定,相對於上述氯乙烯樹脂100質量份,過氯酸處理之水滑石之含有量以0.5質量份以上為佳,以1質量份以上為較佳,且以7質量份以下為佳,以6質量份以下為較佳。過氯酸處理之水滑石之含有量若為上述範圍,則能夠對於由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體更為良好地維持低溫下之延展性。
<<沸石>>
氯乙烯樹脂組成物得以含有沸石作為穩定劑。沸石為以一般式:Mx/n
‧[(AlO2
)x
‧(SiO2
)y
]‧zH2
O(一般式中,M為原子價n之金屬離子,x+y為每單位晶格之四面體數,z為水之莫耳數)式表示之化合物。該一般式中之M之種類可列舉有Na、Li、Ca、Mg、Zn等之一價或二價之金屬或此些之混合型。
於此,沸石之含有量並未特別限定,相對於氯乙烯樹脂100質量份,沸石之含有量以0.1質量份以上為佳,且以5質量份以下為佳。
<<β-二酮>>
β-二酮用以更有效果地抑制由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之初期色調之變動。β-二酮之具體範例可列舉有二苯甲醯甲烷(dibenzoyl methane)、硬脂醯苯甲醯甲烷(stearoylbenzoyl methane)、棕櫚醯苯甲醯甲烷(palmitoylbenzoyl methane)等。此些β-二酮可單獨使用一種,亦可組合二種以上使用。
其中,β-二酮之含有量並未特別限定,相對於氯乙烯樹脂100質量份,β-二酮之含有量以0.1質量份以上為佳,且以5質量份以下為佳。
<<脂肪酸金屬鹽>>
氯乙烯樹脂組成物得以含有之脂肪酸金屬鹽並未特別限定,而能夠為任意的脂肪酸金屬鹽。其中,以一價脂肪酸金屬鹽為佳,以碳原子數為12~24之一價脂肪酸金屬鹽為較佳,以碳原子數為15~21之一價脂肪酸金屬鹽為更佳。脂肪酸金屬鹽之具體範例為硬脂酸鋰、硬脂酸鎂、硬脂酸鋁、硬脂酸鈣、硬脂酸鍶、硬脂酸鋇、硬脂酸鋅、月桂酸鈣、月桂酸鋇、月桂酸鋅、2-乙基己酸鋇、2-乙基己酸鋅、蓖麻酸鋇、蓖麻醇酸鋅等。構成脂肪酸金屬鹽之金屬以可生成多價陽離子之金屬為佳,以可生成二價陽離子之金屬為較佳,以可生成週期表第三週期~第六週期之二價陽離子之金屬為更佳,以可生成週期表第四週期之二價陽離子之金屬為特佳。最佳脂肪酸金屬鹽為硬脂酸鋅。
於此,脂肪酸金屬鹽之含有量並未特別限定,相對於上述氯乙烯樹脂100質量份,脂肪酸金屬鹽之含有量以0.01質量份以上為佳,以0.03質量份以上為較佳,且以5質量份以下為佳,以1質量份以下為較佳,以0.5質量份以下為更佳。其原因在於脂肪酸金屬鹽之含有量若為上述範圍,則能夠縮小由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之色差數值。
<<離型劑>>
離型劑並未特別限定,而例如列舉有12-羥基硬脂酸、12-羥基硬脂酸酯及12-羥基硬脂酸寡聚物等之12-羥基硬脂酸系潤滑劑。於此,離型劑之含有量並未特別限定,相對於上述氯乙烯樹脂100質量份,離型劑之含有量能夠以0.01質量份以上且為5質量份以下。
<<其他除塵劑>>
氯乙烯樹脂組成物得以含有之上述氯乙烯樹脂微粒子以外之其他除塵劑,可列舉有碳酸鈣、滑石、氧化鋁等之無機微粒子;聚丙烯腈樹脂微粒子、聚(甲基)丙烯酸酯樹脂微粒子、聚苯乙烯樹脂微粒子、聚乙烯樹脂微粒子、聚丙烯樹脂微粒子、聚酯樹脂微粒子、聚醯胺樹脂微粒子等之有機微粒子。其中,以平均粒徑為10 nm以上且為100 nm以下之無機微粒子為佳。
於此,其他除塵劑之含有量並未特別限定,相對於氯乙烯樹脂100質量份,其他除塵劑之含有量以30質量份以下為佳,以25質量份以下為較佳。其他除塵劑可單獨使用一種,亦可組合二種以上併用,而且亦可與上述氯乙烯樹脂微粒子併用。
<<其他添加劑>>
氯乙烯樹脂組成物得以含有之其他添加劑並未特別限定,可例如列舉有著色劑(顏料)、耐衝擊性改良劑、過氯酸處理之水滑石以外之過氯酸化合物(過氯酸鈉、過氯酸鉀等)、抗氧化劑、防黴劑、阻燃劑、靜電防止劑、填充劑、光穩定劑、發泡劑等。
著色劑(顏料)之具體範例為喹吖啶酮(quinacridone)系顏料、苝(perylene)系顏料、多偶氮(polyazo)縮合顏料、異吲哚啉酮(isoindolinone)系顏料、銅酞青(copper phthalocyanine)系顏料、鈦白、碳黑。可使用一種或二種以上之顏料。
喹吖啶酮系顏料可由濃硫酸處理對苯二鄰胺苯甲酸(p-phenylene dianthranilic acid)類而獲得,且顯示由黃味紅色至紅味紫色之色相。喹吖啶酮系顏料之具體範例為喹吖啶酮紅、喹吖啶酮洋紅、喹吖啶酮紫。
苝系顏料可藉由苝-3,4,9,10-四羧酸酐與芳香族伯胺之縮合反應而獲得,且顯示由紅色至紅紫色、茶色之色相。苝系顏料之具體範例為苝紅、苝橙、苝栗(perylene maroon)、苝朱紅(perylene vermillion)、苝波爾多紅(perylene bordeaux)。
多偶氮縮合顏料可於溶劑中縮合並高分子量化偶氮色素而獲得,且顯示黃色、紅色系顏料之色相。多偶氮縮合顏料之具體範例為多偶氮紅、多偶氮黃、固美透(Cromophtal)橙、固美透紅、固美透猩紅(Cromophtal scarlet)。
異吲哚啉酮系顏料可藉由4,5,6,7-四氯異吲哚啉酮與芳香族伯二胺(primary aromatic diamine)之縮合反應而獲得,且顯示自綠味黃色至紅色、褐色之色相。異吲哚啉酮系顏料之具體範例為異吲哚啉酮黃。
銅酞青系顏料為於酞青類配位銅之顏料,且顯示自黃味綠色至亮青色之色相。銅酞青系顏料之具體範例為酞青綠、酞青藍。
鈦白為由二氧化鈦而成之白色顏料,遮蓋力強,且有銳鈦礦型和金紅石型。
碳黑為以碳元素為主成分且含有氧元素、氫元素、氮原子之黑色顏料。碳黑之具體範例為熱黑、乙炔黑、通道黑、爐黑、燈黑、骨黑。
耐衝擊性改良劑之具體範例為丙烯腈-丁二烯-苯乙烯共聚物、甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物、氯化聚乙烯、乙烯-乙酸乙烯酯共聚物、氯磺化聚乙烯等。於氯乙烯樹脂組成物能夠使用一種或二種以上之耐衝擊性改良劑。其中,耐衝擊性改良劑成為微細的彈性粒子之不均勻相而分散於氯乙烯樹脂組成物中。於氯乙烯樹脂組成物中,接枝聚合至該彈性粒子之鏈及極性基與氯乙烯樹脂相容,且提升由氯乙烯樹脂組成物成形而成之氯乙烯樹脂成形體之耐衝擊性。
抗氧化劑的具體範例為酚系抗氧化劑、硫系抗氧化劑、亞磷酸鹽等之磷系抗氧化劑等。
防黴劑之具體範例為脂肪族酯系防黴劑、烴系防黴劑、有機氮系防黴劑、有機氮硫系防黴劑等。
阻燃劑之具體範例為鹵素系阻燃劑;磷酸酯等之磷系阻燃劑;氫氧化鎂,氫氧化鋁等之無機氫氧化物等。
靜電防止劑之具體範例為脂肪酸鹽類、高級醇硫酸酯類、磺酸鹽類等之陰離子系靜電防止劑;脂肪族胺鹽類、季胺鹽類等之陽離子靜電防止劑;聚氧乙烯烷基醚類、聚氧乙烯烷基酚醚類等之非離子系靜電防止劑等。
填充劑之具體範例為二氧化矽、滑石、雲母、碳酸鈣、黏土等。
光穩定劑之具體範例為苯並三唑(benzotriazole)系、二苯甲酮(benzophenone)系、鎳螯合系等之紫外線吸收劑,受阻胺系光穩定劑等。
發泡劑之具體範例為偶氮二甲醯胺(azodicarbonamide)、偶氮二異丁腈(azobisisobutyronitrile)等之偶氮化合物、N,N’-二亞硝基五亞甲基四胺(N, N’-dinitroso pentamethylene tetramine)等之亞硝基化合物、對甲苯磺醯肼(p-toluenesulfonylhydrazide)、對,對-氧代雙(苯磺醯肼)(p, p-oxybis(benzenesulfonyl hydrazide))等之磺醯肼化合物等之有機發泡劑;氟利昂氣體、二氧化碳氣體、水、戊烷等之揮發性烴化合物、內包此些材質之微囊等之氣體系發泡劑等。
<氯乙烯樹脂組成物之調製方法>
本發明之氯乙烯樹脂組成物並未特別限定,且能夠混合上述成分而調製出氯乙烯樹脂組成物。
於此,上述氯乙烯樹脂、塑化劑、醚改質矽油、依據需求而更併用之脂肪酸醯胺改質矽油、未改質矽油等之其他矽油、各種添加劑之混合方法並未特別限定,例如列舉有藉由乾摻(dry blend)而混合排除含有氯乙烯樹脂微粒子之除塵劑之成分,且於之後添加、混合除塵劑之方法。於此,乾摻步驟以使用亨歇爾混合機(Henschel mixer)為佳。而且,乾摻時之溫度並未特別限定,以攝氏50度以上為佳,以攝氏70度以上為較佳,且以攝氏200度以下為佳。
<氯乙烯樹脂組成物之用途>
並且,所得到之氯乙烯樹脂組成物能夠適用於粉體成形,且能夠更為適用於粉末搪塑成形。
(氯乙烯樹脂成形體)
本發明之氯乙烯樹脂成形體之特徵在於,藉由利用任意的粉體成形方法,優選為利用粉末搪塑成形方法,以令上述之氯乙烯樹脂組成物成形,進而獲得氯乙烯樹脂成形體。並且,本發明之氯乙烯樹脂成形體因由本發明之氯乙烯樹脂組成物粉體成形而成,而實現良好的表面滑順性,且同時例如能夠既抑制發泡聚胺酯成形體中之空隙產生,亦令發泡聚胺酯成形體良好地背襯於氯乙烯樹脂成形體。因此,本發明之氯乙烯樹脂成形體可作為汽車內裝構材,具體例如適用於汽車儀表板及車門裝飾等之汽車內裝構件之表皮,特別適用於汽車儀表板之表皮用途。
<<氯乙烯樹脂成形體之成形方法>>
於此,粉末搪塑成形時之模具溫度並未特別限定,以攝氏200度以上者為佳,以攝氏220度以上者為較佳,且以攝氏300度以下者為佳,以攝氏280度以下者為較佳。
並且,於製造氯乙烯樹脂成形體時並未特別限定,例如能夠使用以下方法。亦即,將本發明之氯乙烯樹脂組成物灑在上述溫度範圍之模具,於放置5秒鐘以上且30秒鐘以下之期間之後,抖落剩餘的氯乙烯樹脂組成物,再於任意溫度下放置30秒鐘以上且3分鐘以下之期間。之後,將模具冷卻至攝氏10度以上且攝氏60度以下,再自模具脫模所得到之氯乙烯樹脂成形體。並且,脫模之氯乙烯樹脂成形體例如得以作為隨模具之形狀塑形之片狀成形體。
(堆疊體)
本發明之堆疊體具有發泡聚胺酯成形體及上述氯乙烯樹脂成形體。其中,發泡聚胺酯成形體通常背襯於氯乙烯樹脂成形體,發泡聚胺酯成形體及氯乙烯樹脂成形體鄰接於堆疊方向。並且,本發明之堆疊體因具有由本發明之氯乙烯樹脂組成物粉體成形而成之氯乙烯樹脂成形體,故可充分降低表面發黏現象,且於抑制發泡聚胺酯成形體產生空隙的同時還令發泡聚胺酯成形體良好地堆疊於氯乙烯樹脂成形體。因此,本發明之堆疊體例如適用於作為所謂汽車儀表板及車門裝飾等之汽車內裝構件之汽車內裝材,特別適用於汽車儀表板用途。
於此,堆疊方法並未特別限定,例如能夠使用以下方法。亦即,藉由在氯乙烯樹脂成形體上令作為發泡聚胺酯成形體原料之異氰酸酯類及多元醇類等反應以進行聚合的同時,還藉由公知方法進行聚胺酯之發泡,而於氯乙烯樹脂成形體上直接形成發泡聚胺酯成形體。
以下將說明實施例。
以下雖將基於實施例而具體說明本發明,但本發明並非限定於此些實施例。此外,於以下說明中,除非特別說明,否則表示份量之「%」及[份]係以質量為基準。
並且,氯乙烯樹脂粒子及氯乙烯樹脂微粒子之平均聚合度、平均粒子徑;各種矽油之HLB值、動黏度;氯乙烯樹脂成形體之初期及加熱(熱老化試驗)後之於低溫的延展性;氯乙烯樹脂成形體之表面滑順性(動摩擦係數);堆疊體中之發泡聚胺酯成形體中之空隙的產生程度,係使用下述方法量測及評價。
<平均聚合度>
以JIS K6720-2為基準,藉由分別將氯乙烯樹脂粒子及氯乙烯樹脂微粒子溶解於環己酮(cyclohexanone)且分別量測黏度,而算出氯乙烯樹脂粒子及氯乙烯樹脂微粒子之平均聚合度。
<平均粒子徑>
以JIS Z8825為基準量測氯乙烯樹脂粒子及氯乙烯樹脂微粒子之平均粒子徑(體積平均粒子徑(μm))。具體而言,將氯乙烯樹脂粒子及氯乙烯樹脂微粒子分別分散於水槽內,並使用以下所示之裝置量測‧分析光之繞射‧散射強度分布,且量測粒子徑及體積基準之粒子徑分布,藉以算出平均粒子徑。
‧裝置:雷射繞射式粒度分布量測機(島津製作所製之SALD-2300)
‧量測方式:雷射繞射及散射
‧量測範圍:0.017 μm~2500 μm
‧光源:半導體雷射(波長680 nm,輸出3 mW)
<HLB值>
藉由格利分法,依照下述式(3):HLB值=20×(鏈狀環氧乙烷構造之式量之總和/分子量) …(3),而算出各種矽油之HLB值。
HLB值愈高(愈接近20之程度)則矽油之極性愈高而表示為親水性,HLB值愈低(愈接近0之程度)則矽油之極性愈低而表示為親油性。
<動黏度>
各種矽油之動黏度係依照ASTM D 445-46T使用烏氏(Ubbelohde)黏度計,而量測溫度為攝氏25度時之動黏度ηCS / 25
(單位:mm2
/s=cSt(亦有稱為「cs」之情形))。
<低溫時之延展性>
如同以下所述,藉由分別針對初期(成形後未加熱)及加熱(熱老化試驗)後之狀態而量測低溫時之拉伸斷裂伸長率(%),以評價氯乙烯樹脂成形體之延展性。
<<初期>>
利用JIS K6251所記載之一號啞鈴沖壓所得到之氯乙烯樹脂成形片,並以JIS K7161為基準,而於每分鐘200 mm之拉伸速度且攝氏負35度之低溫下量測拉伸斷裂伸長率(%)。拉伸斷裂伸長率之數值愈大,則初期(成形後未加熱)之氯乙烯樹脂成形體具有優良的低溫延展性。
<<加熱(熱老化試驗)後>>
試料為背襯有發泡聚胺酯成形體之堆疊體。將該試料置入烘箱中,並於攝氏130度之環境下加熱100小時。接下來,自加熱後之堆疊體剝離發泡聚胺酯成形體,而僅準備氯乙烯樹脂成形片。並且,藉由與上述初期情況相同的條件,而量測加熱100小時後之氯乙烯樹脂成形片之拉伸斷裂伸長率(%)。拉伸斷裂伸長率之數值愈大,則加熱(熱老化試驗)後之氯乙烯樹脂成形體具有優良的低溫延展性。
<表面滑順性>
如同以下所述,藉由量測動摩擦係數而評價氯乙烯樹脂成形體之表面滑順性。
具體而言,使用質地測試儀(TRINITY-LAB公司製造,商品名「TL201Ts」),於溫度為攝氏23度且相對濕度為50%之量測環境下,於50公克之荷重、每秒鐘10 mm之速度、50 mm之試驗範圍、排除試驗範圍前後10 mm之30 mm之量測範圍之條件下,藉由令觸覺接觸探頭接觸於形成堆疊體前之氯乙烯樹脂成形片,而量測該成形片表面之動摩擦係數。動摩擦係數之數值愈小,氯乙烯樹脂成形體之表面滑順性愈優良,且愈可良好地抑制表面發黏現象。
<空隙的產生程度>
如同以下所述評價堆疊體中之發泡聚胺酯成形體中之空隙的產生程度。
亦即,自堆疊體剝離氯乙烯樹脂成形片,且僅準備發泡聚胺酯成形體(200 mm×300 mm×10 mm)作為試料。接下來,以50 mm之間隔沿短邊方向切斷(六段分割)該試料,且以目視確認剖面的狀態。具體而言,將直徑3 mm以上之孔洞視為空隙,且計算存在於經過六段分割之六個剖面之空隙的總和數量(N1
)。
另一方面,除了氯乙烯樹脂成形片未載置於模具中以外,其餘皆藉由與實施例1之「堆疊體之形成」同樣之步驟製作發泡聚胺酯成形體,並與上述同樣地六段分割該發泡聚胺酯成形體,且計算存在於六個剖面之空隙的總和數量(N0
)。其中,N0
並非計算源自於氯乙烯樹脂成形體之空隙之數量,而是計算源自於形成發泡聚胺酯成形體之操作程序之空隙之數量。而且,於各個試料中,算出以N0
作為基準(100%)之空隙產生率(%)=N1
/N0
× 100,且依照以下之基準評價空隙的產生程度。空隙的產生率愈低(愈接近100%),鄰接於氯乙烯樹脂成形體而被堆疊的發泡聚胺酯成形體中愈難以生成空隙。
A:空隙之產生率未達120%
B:空隙之產生率為120%以上且未達150%
C:空隙之產生率為150%以上
其中,空隙之產生率未達100%之情況視為量測誤差,且被包含於上述A評價中。
(實施例1)
<氯乙烯樹脂組成物之調製>
表1所示之調配成分中,將排除塑化劑(偏苯三酸酯與環氧化大豆油)及作為除塵劑之氯乙烯樹脂微粒子之成分置入亨歇爾混合機並予以混合。接下來,於將混合物之溫度上升至攝氏80度之時間點添加上述全部塑化劑,且藉由更進一步升溫而予以乾燥(作為氯乙烯樹脂之氯乙烯樹脂粒子吸收塑化劑,而意味著上述混合物呈現乾爽狀態)。之後,於將乾燥的混合物冷卻至溫度為攝氏100度以下之時間點添加作為除塵劑之氯乙烯樹脂微粒子,而調製出氯乙烯樹脂組成物。
<氯乙烯樹脂成形體之形成>
將上述所得到之氯乙烯樹脂組成物灑在加熱至溫度為攝氏250度之具皺紋模具,放置於8秒鐘~20秒鐘程度之任意時間以使其熔化之後,抖落剩餘的氯乙烯樹脂組成物。之後,再將灑有該氯乙烯樹脂組成物之具皺紋模具靜置於溫度設定為攝氏200度之烘箱內,於自靜置起算經過60秒鐘之時間點使用冷卻水冷卻具皺紋模具。於模具溫度冷卻至攝氏40度之時間點,自模具脫模作為氯乙烯樹脂成形體之200 mm×300 mm×1 mm之氯乙烯樹脂成形片。並且,依照上述方法針對所得到之氯乙烯樹脂成形片量測、算出初期(成形後未加熱)之低溫時之延展性及表面滑順性(動摩擦係數)。結果如表1所示。
<堆疊體之形成>
所得到之氯乙烯樹脂成形片於溫度設定為攝氏100度之烘箱中靜置二小時,之後其具皺紋之面朝下而敷設於200 mm×300 mm×10 mm之模具中。
另外,混合50份之丙二醇之PO(環氧丙烷)‧EO(環氧乙烷)嵌段加成物(羥基價28,末端EO單位之含有量=10%,內部EO單位之含有量=4%)、50份之甘油之PO‧EO嵌段加成物(羥基價21,末端EO單位之含有量=14%)、2.5份之水、0.2份之三乙二胺(triethylene diamine)之乙二醇溶液(TOSOH公司製造,商品名「TEDA-L33」)、1.2份之三乙醇胺(triethanol amine)、0.5份之三乙胺(triethyl amine)及0.5份之泡沫穩定劑(信越化學工業公司製造,商品名「F-122」),而得到多元醇混合物。而且,調製出混合液,其中此混合液為以令異氰酸酯指數為98之比例混合所得到之多元醇混合物及聚亞甲基聚伸苯基聚異氰酸酯(聚合的MDI)之混合液。並且,氯乙烯樹脂成形片如同以上所述敷設於模具中,且將所調製之混合液灌注於所述之氯乙烯樹脂成形片之上。之後,以348 mm×255 mm×10 mm之鋁板覆蓋於上述模具,以密封模具。藉由自密封模具起算放置5分鐘,而於模具內形成堆疊體。所述堆疊體中,發泡聚胺酯成形體鄰接於作為表皮之氯乙烯樹脂成形片(厚度為1 mm),且發泡聚胺酯成形體(厚度為9 mm,密度為0.18 g/cm3
)背襯(堆疊)於所述氯乙烯樹脂成形片。
接下來,自模具取出所形成之堆疊體,且依照上述方法量測、評價加熱(熱老化試驗)後之低溫時之延展性及空隙之產生程度。結果如表1所示。
(實施例2)
氯乙烯樹脂組成物之調製中,如同表1所示之調配成分,使用0.2份之醚改質矽油B替換0.3份之醚改質矽油A。除了上述以外,其餘皆與實施例1同樣地製造氯乙烯樹脂組成物、氯乙烯樹脂成形片及堆疊體。
接下來,藉由與實施例1同樣的方法進行量測、評價。結果如表1所示。
(實施例3)
氯乙烯樹脂組成物之調製中,如同表1所示之調配成分,使用0.4份之醚改質矽油B替換0.3份之醚改質矽油A。除了上述以外,其餘皆與實施例1同樣地製造氯乙烯樹脂組成物、氯乙烯樹脂成形片及堆疊體。
接下來,藉由與實施例1同樣的方法進行量測、評價。結果如表1所示。
(實施例4)
氯乙烯樹脂組成物之調製中,如同表1所示之調配成分,使用0.2份之醚改質矽油C替換0.3份之醚改質矽油A。除了上述以外,其餘皆與實施例1同樣地製造氯乙烯樹脂組成物、氯乙烯樹脂成形片及堆疊體。
接下來,藉由與實施例1同樣的方法進行量測、評價。結果如表1所示。
(實施例5)
氯乙烯樹脂組成物之調製中,如同表1所示之調配成分,將醚改質矽油A之份量變更為0.2份,且併用0.1份之脂肪酸醯胺改質矽油。除了上述以外,其餘皆與實施例1同樣地製造氯乙烯樹脂組成物、氯乙烯樹脂成形片及堆疊體。
接下來,藉由與實施例1同樣的方法進行量測、評價。結果如表1所示。
(比較例1)
氯乙烯樹脂組成物之調製中,未使用任何矽油。而且,如同表1所示之調配成分,將氯乙烯樹脂微粒子A之調配份量自8份變更為10份,且使用10份之氯乙烯樹脂微粒子C替換8份之氯乙烯樹脂微粒子B。除了上述以外,其餘皆與實施例1同樣地製造氯乙烯樹脂組成物、氯乙烯樹脂成形片及堆疊體。
接下來,藉由與實施例1同樣的方法進行量測、評價。結果如表1所示。
(比較例2)
氯乙烯樹脂組成物之調製中,如同表1所示之調配成分,使用0.4份之未改質矽油替換0.3份之醚改質矽油A。而且,如同表1所示之調配成分,將氯乙烯樹脂微粒子A之調配份量自8份變更為10份,且使用10份之氯乙烯樹脂微粒子C替換8份之氯乙烯樹脂微粒子B。除了上述以外,其餘皆與實施例1同樣地製造氯乙烯樹脂組成物、氯乙烯樹脂成形片及堆疊體。
接下來,藉由與實施例1同樣的方法進行量測、評價。結果如表1所示。
(比較例3)
氯乙烯樹脂組成物之調製中,如同表1所示之調配成分,使用0.4份之矽烷醇改質矽油替換0.3份之醚改質矽油A。而且,如同表1所示之調配成分,將氯乙烯樹脂微粒子A之調配份量自8份變更為10份,且使用10份之氯乙烯樹脂微粒子C替換8份之氯乙烯樹脂微粒子B。除了上述以外,其餘皆與實施例1同樣地製造氯乙烯樹脂組成物、氯乙烯樹脂成形片及堆疊體。
接下來,藉由與實施例1同樣的方法進行量測、評價。結果如表1所示。
(比較例4)
氯乙烯樹脂組成物之調製中,如同表1所示之調配成分,使用0.2份之脂肪酸醯胺改質矽油替換0.3份之醚改質矽油A。除了上述以外,其餘皆與實施例1同樣地製造氯乙烯樹脂組成物、氯乙烯樹脂成形片及堆疊體。
接下來,藉由與實施例1同樣的方法進行量測、評價。結果如表1所示。
表1
1)新第一氯乙烯公司製造,商品名「ZEST(註冊商標) 1700ZI」(懸浮聚合法,平均聚合度:1700,平均粒子徑:130 μm)
2)新第一氯乙烯公司製造,商品名「ZEST PQLTX」(乳化聚合法,平均聚合度:800,平均粒子徑:1.8 μm)
3)TOSOH公司製造,商品名「Ryuron Paste(註冊商標) 860」(乳化聚合法,平均聚合度:1600,平均粒子徑:1.6 μm)
4)TOSOH公司製造,商品名「Ryuron Paste(註冊商標) 761」(乳化聚合法,平均聚合度:2100,平均粒子徑:1.6 μm)
5)花王公司製造,商品名「TRIMEX N-08」
6)ADEKA公司製造,商品名「AKEDA CIZER-O-130S」
7)信越化學工業公司製造,商品名「F242TL」(醚改質矽油[將具有鏈狀環氧乙烷構造及鏈狀環氧丙烷構造之醚基導入至側鏈而成],HLB值:6,於攝氏25度之動黏度:1000 cSt)
8)信越化學工業公司製造,商品名「X-50-1039A」(醚改質矽油[將具有鏈狀環氧乙烷構造及鏈狀環氧丙烷構造之醚基導入至側鏈而成],HLB值:2,於攝氏25度之動黏度:500 cSt)
9)信越化學工業公司製造,商品名「X-22-2516」(醚改質矽油[將具有鏈狀環氧乙烷構造、鏈狀環氧丙烷構造及有機構造之醚基導入至分別相異於長鏈烷基及芳烷基之部位之側鏈而成],HLB值:1,於攝氏25度之動黏度:70 cSt)
10)信越化學工業公司製造,商品名「KF-3935」(高級脂肪酸醯胺改質矽油[導入有脂肪酸醯胺基而成],HLB值:0,於常溫常壓下為膠狀)
11)信越化學工業公司製造,商品名「KF-96」(未改質矽油,HLB值:0,於攝氏25度之動黏度:5000 cSt)
12)信越化學工業公司製造,商品名「KF-9701」(矽烷醇改質矽油,HLB值:0,於攝氏25度之動黏度:60 cSt)
13)協和化學工業公司製造,商品名「ALCAMIZER(註冊商標) 5」
14)水澤化學工業公司製造,商品名「MIZUKALIZER DS」
15)昭和電工公司製造,商品名「Karenz DK-1」
16)堺化學工業公司製造,商品名「SAKAI SZ2000」
17)ADEKA公司製造,商品名「AKEDA STAB LS-12」
18)大日精化公司製造,商品名「DA PX 1720(A) BLACK」
由表1可知,於未使用醚改質矽油之比較例1~4中,無法兼顧氯乙烯樹脂片之優良的表面滑順性及被堆疊於氯乙烯樹脂片之發泡聚胺酯成形體中之空隙產生之抑制。
更具體而言,於未使用任何矽油之比較例1中,可知鄰接且被堆疊於氯乙烯樹脂片之發泡聚胺酯成形體中雖未產生空隙,但氯乙烯樹脂片之表面滑順性顯為劣等。而且,可知於僅使用未改質矽油、僅使用矽烷醇改質矽油及僅使用脂肪酸醯胺改質矽油作為矽油之比較例2~4中,氯乙烯樹脂片雖具有優良的表面滑順性,但鄰接且被堆疊於氯乙烯樹脂片之發泡聚胺酯成形體中卻容易產生空隙。
相對於此,可知包含氯乙烯樹脂、塑化劑及矽油且該矽油至少包含醚改質矽油之實施例1~5中,氯乙烯樹脂片能夠具有優良的表面滑順性,且能夠良好地抑制被堆疊於氯乙烯樹脂片之發泡聚胺酯成形體中產生空隙。
若根據本發明,則能夠提供氯乙烯樹脂成形體及能夠製造該氯乙烯樹脂成形體之氯乙烯樹脂組成物,而得以具有優良的表面滑順性,且得以抑制被堆疊的發泡聚胺酯成形體中產生空隙。
而且,若根據本發明,則能夠提供具有發泡聚胺酯成形體及氯乙烯樹脂成形體之堆疊體,其可具有優良的表面滑順性,且可抑制空隙之產生。
無
無。
Claims (13)
- 一種氯乙烯樹脂組成物,包括:一氯乙烯樹脂;一塑化劑;以及一矽油,其中該矽油至少包括一醚改質矽油。
- 如請求項1所述之氯乙烯樹脂組成物,其中該醚改質矽油之HLB值為3以下。
- 如請求項1所述之氯乙烯樹脂組成物,其中該矽油更包括一脂肪酸醯胺改質矽油及一未改質矽油之至少一者。
- 如請求項3所述之氯乙烯樹脂組成物,其中該醚改質矽油之含有量大於該脂肪酸醯胺改質矽油之含有量及該未改質矽油之含有量之總和。
- 如請求項3或4所述之氯乙烯樹脂組成物,其中該醚改質矽油之HLB值為4以上。
- 如請求項1所述之氯乙烯樹脂組成物,其中該醚改質矽油之一主鏈由矽氧烷鍵結而成,且該醚改質矽油由將一醚基導入至該主鏈、該主鏈之一側鏈及該主鏈之一末端之至少一者而成,該醚基具有以一般式(1)及一般式(2)表示之構造,且無不飽和鍵,其中:-(C2 H4 O)x - (1),於式(1)中之x為1以上之自然數;-(C3 H6 O)y - (2),於式(2)中之y為1以上之自然數。
- 如請求項1所述之氯乙烯樹脂組成物,其中該醚改質矽油之動黏度為65 cSt以上。
- 如請求項1所述之氯乙烯樹脂組成物,其中相對於該氯乙烯樹脂為100質量份,該塑化劑之含有量為70質量份以上。
- 如請求項1所述之氯乙烯樹脂組成物,其中該氯乙烯樹脂組成物使用於粉末成形。
- 如請求項9所述之氯乙烯樹脂組成物,其中該氯乙烯樹脂組成物使用於粉末搪塑(powder slush)成形。
- 一種氯乙烯樹脂成形體,由如請求項9或10所述之氯乙烯樹脂組成物成形而成。
- 如請求項11所述之氯乙烯樹脂成形體,其中該氯乙烯樹脂成形體為用於汽車儀表板表皮。
- 一種堆疊體,包括:一發泡聚胺酯成形體;以及如請求項11或12所述之氯乙烯樹脂成形體。
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| JP7786106B2 (ja) * | 2021-09-30 | 2025-12-16 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 |
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| US2789100A (en) * | 1953-02-24 | 1957-04-16 | Union Carbide & Carbon Corp | Stabilized vinyl chloride compositions |
| US3795634A (en) * | 1972-05-03 | 1974-03-05 | Gen Electric | Vinyl chloride foam containing silicone polymers |
| DE2712688C3 (de) * | 1977-03-23 | 1979-10-04 | Dynamit Nobel Ag, 5210 Troisdorf | Losungsmittelfreie Formmasse auf Basis Polyvinylchlorid |
| JPS61174270A (ja) | 1985-01-29 | 1986-08-05 | Kyowa Chem Ind Co Ltd | 耐発錆性ないし耐着色性賦与剤 |
| JP2821746B2 (ja) * | 1988-06-01 | 1998-11-05 | 豊田合成 株式会社 | 塩化ビニル樹脂系組成物 |
| JPH0275647A (ja) * | 1988-09-12 | 1990-03-15 | Shin Etsu Chem Co Ltd | 塩化ビニル樹脂製シート |
| JPH0439344A (ja) * | 1990-06-05 | 1992-02-10 | Kanegafuchi Chem Ind Co Ltd | 樹脂組成物 |
| JPH0867774A (ja) * | 1994-08-29 | 1996-03-12 | C I Kasei Co Ltd | 農業用合成樹脂被覆材 |
| JP2003048281A (ja) | 2001-08-06 | 2003-02-18 | C I Kasei Co Ltd | 防塵性農業用塩化ビニル系樹脂フイルム |
| ITMI20061107A1 (it) * | 2006-06-08 | 2007-12-09 | Diab Int Ab | Formulazioni per prodotti cellulari di polimero espanso basati su polivinl cloruro prodotti cellulari di polimero espanso migliorati basati su polivinil cloruro e processo per produrre detti prodotti cellulari di polimero espanso migliorati |
| JP4798396B2 (ja) * | 2008-07-07 | 2011-10-19 | 信越化学工業株式会社 | 水中生物付着防止塗料組成物及びそれを用いた水中構造物 |
| WO2010117020A1 (ja) * | 2009-04-08 | 2010-10-14 | テクノポリマー株式会社 | 軋み音を低減した自動車内装部品 |
| JP5500519B2 (ja) * | 2009-07-30 | 2014-05-21 | 株式会社アイ・イー・ジェー | 発泡ウレタン複合成形品の製造方法および発泡ウレタン複合成形品 |
| JP5360422B2 (ja) | 2010-02-24 | 2013-12-04 | 日本ゼオン株式会社 | 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体及び積層体 |
| JP5435238B2 (ja) | 2010-06-23 | 2014-03-05 | 日本ゼオン株式会社 | 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体及び積層体 |
| WO2012020618A1 (ja) * | 2010-08-12 | 2012-02-16 | 日本ゼオン株式会社 | 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体及び積層体 |
| JP2014005449A (ja) | 2012-05-29 | 2014-01-16 | Sanyo Chem Ind Ltd | スラッシュ成形用熱可塑性樹脂粒子組成物 |
| CN103804889B (zh) * | 2014-02-18 | 2016-01-27 | 山东美瑞新材料有限公司 | 一种发泡热塑性聚氨酯粒子及其制备方法和应用 |
| JP6448370B2 (ja) * | 2015-01-08 | 2019-01-09 | 株式会社Adeka | 難燃剤組成物及び難燃性合成樹脂組成物 |
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| JP7088018B2 (ja) | 2022-06-21 |
| EP3521362B1 (en) | 2023-02-22 |
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| CA3038626A1 (en) | 2018-04-05 |
| WO2018061859A1 (ja) | 2018-04-05 |
| CN109844014A (zh) | 2019-06-04 |
| JPWO2018061859A1 (ja) | 2019-07-04 |
| KR20190056375A (ko) | 2019-05-24 |
| CN109844014B (zh) | 2022-04-01 |
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