JP6432935B2 - Vinyl chloride resin sheet - Google Patents
Vinyl chloride resin sheet Download PDFInfo
- Publication number
- JP6432935B2 JP6432935B2 JP2014235249A JP2014235249A JP6432935B2 JP 6432935 B2 JP6432935 B2 JP 6432935B2 JP 2014235249 A JP2014235249 A JP 2014235249A JP 2014235249 A JP2014235249 A JP 2014235249A JP 6432935 B2 JP6432935 B2 JP 6432935B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- base material
- material layer
- plasticizer
- 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.)
- Active
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- 239000011347 resin Substances 0.000 title claims description 42
- 229920005989 resin Polymers 0.000 title claims description 42
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 40
- 239000004014 plasticizer Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 25
- 239000002216 antistatic agent Substances 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 239000010410 layer Substances 0.000 description 42
- -1 phosphate ester Chemical class 0.000 description 31
- 229910019142 PO4 Inorganic materials 0.000 description 19
- 239000010452 phosphate Substances 0.000 description 19
- 239000003063 flame retardant Substances 0.000 description 12
- 239000003999 initiator Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 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 8
- 239000000178 monomer Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 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
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 description 3
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 2
- GLYJVQDYLFAUFC-UHFFFAOYSA-N butyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCCCC GLYJVQDYLFAUFC-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 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 2
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-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
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- OZFLRNPZLCUVFP-UHFFFAOYSA-N 8-methylnonyl dihydrogen phosphate Chemical compound CC(C)CCCCCCCOP(O)(O)=O OZFLRNPZLCUVFP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical class C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- UQRSMZHDWDMLDH-UHFFFAOYSA-N bis(2-tert-butylphenyl) phenyl phosphate Chemical compound CC(C)(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)(C)C)OC1=CC=CC=C1 UQRSMZHDWDMLDH-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- UCVPKAZCQPRWAY-UHFFFAOYSA-N dibenzyl benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC=2C=CC=CC=2)C=1C(=O)OCC1=CC=CC=C1 UCVPKAZCQPRWAY-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 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
- 238000003912 environmental pollution Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 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
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 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
- SPUXJWDKFVXXBI-UHFFFAOYSA-N tris(2-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)(C)C)OC1=CC=CC=C1C(C)(C)C SPUXJWDKFVXXBI-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は塩化ビニル系樹脂シートに関する。 The present invention relates to a vinyl chloride resin sheet.
合成樹脂は一般に可燃性であるため、電気・電子部品、自動車部材、建築部材等の難燃性を要求される分野においては、他の樹脂に比べて燃焼し難く、機械的な特性も優れた塩化ビニル系樹脂に、更に難燃剤を添加したものが用いられている。塩化ビニル系樹脂に用いられる難燃剤として、ハロゲン系難燃剤や、アンチモン化合物等の無機系難燃剤が知られているが、ハロゲン系難燃剤は環境汚染問題を生じる虞があることから、近年、使用が敬遠されている。また、無機系難燃剤を添加した塩化ビニル系樹脂は白濁するため、透明性を要求される用途には不向きであった。一方、透明性を維持しながら難燃性を付与した塩化ビニル樹脂組成物として、安定剤、可塑剤とともに難燃剤として縮合リン酸エステルを配合したものが提案されている（特許文献１）。 Synthetic resins are generally flammable, so they are less flammable than other resins and have excellent mechanical properties in fields that require flame retardancy, such as electrical and electronic parts, automobile parts, and building parts. The thing which added the flame retardant further to the vinyl chloride-type resin is used. As flame retardants used for vinyl chloride resins, inorganic flame retardants such as halogen flame retardants and antimony compounds are known, but halogen flame retardants may cause environmental pollution problems. Use is avoided. Moreover, since the vinyl chloride resin to which the inorganic flame retardant is added becomes cloudy, it is not suitable for applications requiring transparency. On the other hand, as a vinyl chloride resin composition imparted with flame retardancy while maintaining transparency, a composition in which a condensed phosphate ester is blended as a flame retardant together with a stabilizer and a plasticizer has been proposed (Patent Document 1).
しかしながら、縮合リン酸エステル等のリン酸エステル系難燃剤は、ブリードアウトし易くシート表面にベタつきを生じるとともに、臭気が強いという問題があった。本発明者等はかかる問題を解決すべく鋭意研究した結果、特定のリン酸エステル系化合物を配合した塩化ビニル樹脂系シートが、難燃剤のブリードアウトによるシート表面のベタつきの問題がなく、優れた難燃性を有するとともに、可塑剤の配合量を少なくしても優れた柔軟性を有することを見出し本発明を完成するに至った。 However, phosphoric acid ester flame retardants such as condensed phosphoric acid esters have a problem that they easily bleed out and cause stickiness on the sheet surface and have a strong odor. As a result of intensive studies to solve such problems, the present inventors have found that the vinyl chloride resin-based sheet blended with a specific phosphate ester-based compound has no problem of stickiness of the sheet surface due to the bleed-out of the flame retardant, and is excellent. It has been found that it has flame retardancy and has excellent flexibility even if the blending amount of the plasticizer is reduced, and the present invention has been completed.
即ち本発明は、
（１）基材層と、該基材層の少なくとも片面に設けられたブロック層とからなり、基材層は可塑剤、リン酸トリアリールイソプロピル化物を含有する塩化ビニル系樹脂よりなり、ブロック層はアクリルウレタン系樹脂よりなり、 ブロック層には酸化亜鉛と五酸化アンチモンの複酸化物である帯電防止剤が含有されていることを特徴とする塩化ビニル系樹脂シート、
（２）塩化ビニル系樹脂１００質量部に対して、可塑剤が１０〜７０質量部、リン酸トリアリールイソプロピル化物が１０〜４０質量部含有されてなることを特徴とする上記（１）に記載の塩化ビニル系樹脂シート、
を要旨とするものである。
That is, the present invention
(1) It consists of a base material layer and a block layer provided on at least one surface of the base material layer, and the base material layer is made of a vinyl chloride resin containing a plasticizer and a triaryl isopropylated phosphate, the Ri Na from acrylic urethane resin, vinyl chloride resin sheet is in the block layer, characterized that you have been contained in the antistatic agent is a mixed oxide of zinc oxide and antimony pentoxide,
(2) The plasticizer is contained in an amount of 10 to 70 parts by mass and the triaryl isopropylated product is contained in an amount of 10 to 40 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Vinyl chloride resin sheet,
Is a summary.
本発明の塩化ビニル系樹脂シートは、可塑剤及びリン酸トリアリールイソプロピル化物を含む塩化ビニル系樹脂の基材層の少なくとも片面に、アクリルウレタン系樹脂よりなるブロック層を設けたことにより、難燃性を損なうことなく難燃剤のブリードアウトによるシート表面のベタ付きを抑制し、また可塑化効果を損なうことなく可塑剤の添加量を少なくすることができ、透明性、難燃性に優れるとともに柔軟性に優れる等の効果を奏する。またブロック層中に、酸化亜鉛と五酸化アンチモンの複酸化物を帯電防止剤として含有すると、帯電防止性が向上するだけでなく、難燃剤と相乗的に作用して更に高い難燃性が発揮される等の効果を奏する。 The vinyl chloride resin sheet of the present invention is flame retardant by providing a block layer made of an acrylic urethane resin on at least one surface of a vinyl chloride resin base material layer containing a plasticizer and a triaryl isopropylated phosphate. Suppresses stickiness of the sheet surface due to the bleed-out of the flame retardant without impairing the properties, and can reduce the amount of plasticizer added without impairing the plasticizing effect. Excellent transparency and flame retardancy and flexibility There are effects such as excellent properties. In addition, when the block layer contains a double oxide of zinc oxide and antimony pentoxide as an antistatic agent, it not only improves antistatic properties, but also acts more synergistically with the flame retardant to exhibit even higher flame resistance. The effects such as being done.
本発明の塩化ビニル系樹脂シートにおける基材層に用いられる塩化ビニル系樹脂としては、ポリ塩化ビニル、塩化ビニルモノマーと、該塩化ビニルモノマーと共重合可能な他のモノマーとの共重合体、塩化ビニルモノマーと高級ビニルエーテルとの共重合体等が挙げられる。塩化ビニルモノマーと共重合可能な他のモノマーとしては、例えばエチレン、プロピレン、マレイン酸エステル、メタクリル酸メチル、メタクリル酸エチル、アクリル酸メチル、アクリル酸エチル、メタクリル酸、アクリル酸、酢酸ビニル等のオレフィン系モノマーやアクリル系モノマーが挙げられる。塩化ビニル系樹脂は単独で用いても、二種以上を混合して用いても良い。塩化ビニル系樹脂は、重合度５００〜１５００のものが好ましく、重合度８００〜１３００のものがより好ましい。塩化ビニル系樹脂の重合度が５００未満であると、溶融張力が低いため成形性が低下し、重合度が１５００を超えると加工温度が高くなり樹脂が分解しやすくなる。 Examples of the vinyl chloride resin used for the base material layer in the vinyl chloride resin sheet of the present invention include polyvinyl chloride, copolymers of vinyl chloride monomer and other monomers copolymerizable with the vinyl chloride monomer, chloride Examples thereof include a copolymer of a vinyl monomer and a higher vinyl ether. Examples of other monomers copolymerizable with vinyl chloride monomer include olefins such as ethylene, propylene, maleate, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, and vinyl acetate. And monomers based on acrylic and acrylic monomers. The vinyl chloride resin may be used alone or in combination of two or more. The vinyl chloride resin preferably has a polymerization degree of 500 to 1500, and more preferably a polymerization degree of 800 to 1300. If the degree of polymerization of the vinyl chloride resin is less than 500, the melt tension is low and the moldability is lowered, and if the degree of polymerization exceeds 1500, the processing temperature becomes high and the resin is easily decomposed.
本発明において難燃剤として用いるリン酸トリアリールイソプロピル化物としては、例えばイソプロピルフェニルジフェニルホスフェート（ＩＰＰ）、ビス−（イソプロピルフェニル）ジフェニルホスフェート（ＢＩＰＰ）、トリス−（イソプロピルフェニル）ホスフェート（ＴＩＰＰ）等が挙げられる。リン酸トリアリールイソプロピル化物は、イソプロピル化度の異なる化合物が存在し、イソプロピル化度に比例して粘度が増加する。本発明において、リン酸トリアリールイソプロピル化物は、粘度３０〜１２０（ｍｍ２／ｓ、２５℃）のものが好ましく用いられ、さらに好ましくは粘度４０〜６５である。リン酸トリアリールイソプロピル化物は、他のリン酸エステル系化合物に比べてブリードアウトしにくく、臭気が少なく塩化ビニル系樹脂シートの透明性にも優れる。本発明において、ブリードアウトの問題が生じない範囲において、リン酸トリアリールイソプロピル化物とともに、他のリン酸エステル系化合物を難燃剤として併用することもできる。他のリン酸エステル系化合物としては、トリフェニルホスフェート（ＴＰＰ）、トリキシレニルホスフェート（ＴＸＰ）、クレジルジフェニルホスフェート（ＣＤＰ）、２-エチルヘキシルジフェニルホスフェート（ＥＨＤＰ）、ｔ−ブチルフェニルジフェニルホスフェート（ｔ−ＢＤＰ）、ビス−（ｔ-ブチルフェニル）フェニルホスフェート（ＢＢＤＰ）、トリス−（ｔ-ブチルフェニル）ホスフェート（ＴＢＤＰ）等が挙げられる。 Examples of the triaryl isopropylated product used as a flame retardant in the present invention include isopropylphenyl diphenyl phosphate (IPP), bis- (isopropylphenyl) diphenyl phosphate (BIPP), tris- (isopropylphenyl) phosphate (TIPP), and the like. It is done. Triaryl phosphate isopropylates have compounds with different degrees of isopropylation, and the viscosity increases in proportion to the degree of isopropylation. In the present invention, the triaryl isopropylated phosphate preferably has a viscosity of 30 to 120 (mm 2 / s, 25 ° C.), and more preferably has a viscosity of 40 to 65. Triaryl isopropylates are less likely to bleed out than other phosphate ester compounds, have less odor, and are excellent in transparency of vinyl chloride resin sheets. In the present invention, as long as the problem of bleed-out does not occur, other phosphate ester compounds can be used together with the triaryl isopropylated phosphate as a flame retardant. Other phosphate ester compounds include triphenyl phosphate (TPP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), t-butylphenyl diphenyl phosphate (t -BDP), bis- (t-butylphenyl) phenyl phosphate (BBDP), tris- (t-butylphenyl) phosphate (TBDP) and the like.
基材層中に含有される可塑剤としては、フタル酸ジオクチルエステル（ＤＯＰ）、フタル酸ジイソノニルエステル（ＤＩＮＰ）、フタル酸ベンジルエステル（ＢＢＰ）、フタル酸ジイソデシルエステル（ＤＩＤＰ）、フタル酸ジウンデシルエステル（ＤＵＰ）等に代表されるフタル酸エステル系可塑剤、アジピン酸ジオクチルエステル（ＤＯＡ）、セバシン酸ジオクチル（ＤＯＳ）、アゼライン酸ジオクチルエステル（ＤＯＺ）等に代表される脂肪酸エステル系可塑剤、トリメリット酸トリオクチルエステル系可塑剤、ポリプロピレンアジペート等に代表されるポリエステル系可塑剤などの高分子可塑剤、セバシン酸系可塑剤、塩素化パラフィン等が挙げられる。 Plasticizers contained in the base material layer include dioctyl phthalate (DOP), diisononyl phthalate (DINP), benzyl phthalate (BBP), diisodecyl phthalate (DIDP), and diundecyl phthalate. Phthalate ester plasticizers typified by (DUP), fatty acid ester plasticizers typified by dioctyl adipate (DOA), dioctyl sebacate (DOS), azelaic acid dioctyl ester (DOZ), etc. Examples include acid trioctyl ester plasticizers, polymer plasticizers such as polyester plasticizers typified by polypropylene adipate, sebacic acid plasticizers, and chlorinated paraffins.
基材層中における上記可塑剤と、リン酸トリアリールイソプロピル化物との比率は、質量比で、可塑剤：リン酸トリアリールイソプロピル化物＝７：１〜１：４が好ましい。可塑剤の添加量は、通常、塩化ビニル系樹脂１００質量部に対し、１０〜９０質量部であるが、本発明の塩化ビニル系樹脂シートは、基材層中に可塑剤とともにリン酸トリアリールイソプロピル化物とを含有することにより、可塑剤の使用量を低減することができ、塩化ビニル系樹脂１００質量部あたり、可塑剤１０〜７０質量部、リン酸トリアリールイソプロピル化物１０〜４０質量部が好ましい。リン酸トリアリール化物の添加量が少ないと、十分な難燃性を付与できず、多すぎるとブリードアウトの問題を生じる虞がある。可塑剤とリン酸トリアリールイソプロピル化物とを併用したことにより、可塑剤の添加量を減量しても可塑化効果を維持したまま難燃性を付与することができる。 The ratio of the plasticizer to the triaryl isopropylated product in the base material layer is preferably a mass ratio of plasticizer: triaryl isopropylated product = 7: 1 to 1: 4. The addition amount of the plasticizer is usually 10 to 90 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, but the vinyl chloride resin sheet of the present invention is a triaryl phosphate together with the plasticizer in the base material layer. By containing the isopropylated product, the amount of the plasticizer used can be reduced, and 10 to 70 parts by mass of the plasticizer and 10 to 40 parts by mass of the triaryl isopropylated product per 100 parts by mass of the vinyl chloride resin. preferable. If the added amount of the phosphorylated triarylate is small, sufficient flame retardancy cannot be imparted, and if it is too large, there is a possibility of causing a bleed-out problem. By using the plasticizer and the triaryl isopropylated product in combination, flame retardancy can be imparted while maintaining the plasticizing effect even if the amount of plasticizer added is reduced.
基材層中には、必要に応じて熱安定剤、光安定剤、紫外線吸収剤、酸化防止剤、滑剤、充填剤、着色剤等の添加物が配合されていても良い。熱安定剤としては、例えばエポキシ化大豆油、Ｂａ−Ｚｎ、Ｃａ−Ｚｎ、酸化亜鉛などの金属系安定剤等が、光安定剤としては、例えばヒンダードアミン系化合物等が、紫外線吸収剤としては、例えばベンゾトリアゾール系化合物、トリアジン系化合物等が挙げられる。また酸化防止剤としては、例えばヒンダードフェノール系化合物等が、滑剤としては、例えばステアリン酸などの脂肪酸系滑剤、ステアリン酸アミド、メチレンビスステアロアミドなどの脂肪酸アミド系滑剤、ブチルパルミテートなどのエステル系滑剤、バリウムイソデシルホスフェートなどの有機リン酸金属塩系滑剤、ポリエチレンワックス、流動パラフィン等が、充填剤としては、例えば炭酸カルシウム、炭酸マグネシウム、マグネシウム系ケイ酸塩、酸化アルミニウム、水酸化アルミニウム、水酸化マグネシウム、タルク、ハイドロタルサイトなどの無機質充填剤のほか、架橋塩化ビニル樹脂粉末、アクリル系樹脂粉末、ポリウレタン粉末などの架橋された合成樹脂の粉末などの有機質充填剤等が挙げられる。 In the base material layer, additives such as a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antioxidant, a lubricant, a filler, and a colorant may be blended as necessary. Examples of the heat stabilizer include metal stabilizers such as epoxidized soybean oil, Ba-Zn, Ca-Zn, and zinc oxide. Examples of the light stabilizer include hindered amine compounds. Examples of the ultraviolet absorber include Examples thereof include benzotriazole compounds and triazine compounds. Examples of the antioxidant include hindered phenol compounds, and examples of the lubricant include fatty acid lubricants such as stearic acid, fatty acid amide lubricants such as stearic acid amide and methylenebisstearamide, and butyl palmitate. Ester lubricants, organophosphate metal salt lubricants such as barium isodecyl phosphate, polyethylene wax, liquid paraffin, etc. Examples of fillers include calcium carbonate, magnesium carbonate, magnesium silicate, aluminum oxide, aluminum hydroxide In addition to inorganic fillers such as magnesium hydroxide, talc and hydrotalcite, organic fillers such as crosslinked synthetic resin powders such as crosslinked vinyl chloride resin powder, acrylic resin powder and polyurethane powder can be used.
基材層は、塩化ビニル系樹脂と、可塑剤、リン酸トリアリールイソプロピル化物等の添加剤成分を、スーパーミキサー、ヘンシェルミキサー等で混合し、カレンダー法、押出法、インフレーション法等によりシート状に成形して形成することができる。基材層の厚みは特に限定されないが、０．１〜５．０ｍｍが好ましい。基材層は、塩化ビニル系樹脂シートの単一層からなるものでも、複数層からなるものでも良い。塩化ビニル系樹脂シートの複数層からなる基材層の場合、各層は同一組成であっても、異なる組成であっても良く、各層に含有される可塑剤やリン酸トリアリールイソプロピル化物、その他の添加の添加量を変えて、各層の物性を異なるものとしても良い。 The base material layer is formed by mixing vinyl chloride resin and additive components such as plasticizer and triaryl isopropylate with a super mixer, Henschel mixer, etc., and forming it into a sheet by calendering, extrusion, inflation, etc. It can be formed by molding. Although the thickness of a base material layer is not specifically limited, 0.1-5.0 mm is preferable. The base material layer may be composed of a single layer of a vinyl chloride resin sheet or may be composed of a plurality of layers. In the case of a base material layer composed of a plurality of layers of a vinyl chloride resin sheet, each layer may have the same composition or a different composition, and a plasticizer, a triaryl isopropylated product contained in each layer, other The physical properties of each layer may be different by changing the amount of addition.
ブロック層は、基材層の少なくとも片面に設けられるが、基材層の両面に設けても良い。ブロック層はアクリルウレタン系樹脂塗料を、ナイフコーティング、スプレーコーティング、ロールコーティング、グラビアコーティング、リバースコーティング、ディップコーティング等により基材層上に塗布し、紫外線照射して硬化させることにより形成することができる。本発明の塩化ビニル系樹脂シートにおける基材層中に含まれるリン酸トリアリールイソプロピル化物は他のリン酸エステル系化合物と比較するとブリードアウトし難いが、基材層の少なくとも片面にアクリルウレタン系樹脂よりなるブロック層を形成することにより、基材層からの可塑剤やリン酸トリアリールイソプロピル化物、あるいはその他の添加剤のブリードアウトが、更に確実に防止される。ブロック層の厚みは５〜５０μｍ（乾燥後）であることが好ましい。 The block layer is provided on at least one surface of the base material layer, but may be provided on both surfaces of the base material layer. The block layer can be formed by applying acrylic urethane-based resin paint on the base material layer by knife coating, spray coating, roll coating, gravure coating, reverse coating, dip coating, etc., and curing by ultraviolet irradiation. . The triaryl isopropylated product contained in the base material layer in the vinyl chloride resin sheet of the present invention is less likely to bleed out compared to other phosphate ester compounds, but at least one surface of the base material layer is an acrylic urethane resin. By forming the block layer, bleeding out of the plasticizer, the triaryl isopropylate from the base material, or other additives can be prevented more reliably. The thickness of the block layer is preferably 5 to 50 μm (after drying).
ブロック層を形成するアクリルウレタン系樹脂塗料は、分子中にウレタン結合を有し、かつラジカル重合可能な不飽和二重結合を有する平均分子量数百〜数万程度のアクリルウレタンオリゴマーを主成分とするものである。例えば無黄変型ポリイソシアネートと水酸基を有する（メタ）アクリル酸エステルとの反応によって得られるオリゴマーの他に、ポリエーテル系アクリルウレタンオリゴマー、ポリエステル系アクリルウレタンオリゴマー、ポリブタジエン系アクリルウレタンオリゴマー等が挙げられる。具体的には、トルエンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、キシレンジイソシアネート、これらの異性体あるいは過剰のポリイソシアネートとポリエステルポリオール、ポリオキシメチレングリコール、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、カプロラクトンポリオール、トリメチロールプロパン、ペンタエリスリトールなどの多価アルコールとの反応生成物であるイソシアネート末端を有するアクリル化合物等のポリイソシアネート、好ましくは無黄変型ポリイソシアネートと、水酸基及び不飽和基を有する化合物との反応生成物等が挙げられる。水酸基及び不飽和基を有するアクリル化合物としては、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、グリシジル（メタ）アクリレート等が挙げられる。 The acrylic urethane-based resin coating that forms the block layer is mainly composed of an acrylic urethane oligomer having an average molecular weight of several hundred to several tens of thousands that has a urethane bond in the molecule and an unsaturated double bond capable of radical polymerization. Is. For example, in addition to the oligomer obtained by the reaction of a non-yellowing polyisocyanate and a (meth) acrylic acid ester having a hydroxyl group, a polyether acrylic urethane oligomer, a polyester acrylic urethane oligomer, a polybutadiene acrylic urethane oligomer and the like can be mentioned. Specifically, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, isomers thereof or excess polyisocyanate and polyester polyol, polyoxymethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, caprolactone A polyisocyanate such as an acrylic compound having an isocyanate terminal which is a reaction product with a polyhydric alcohol such as polyol, trimethylolpropane and pentaerythritol, preferably a non-yellowing polyisocyanate, and a compound having a hydroxyl group and an unsaturated group Reaction products etc. are mentioned. Examples of the acrylic compound having a hydroxyl group and an unsaturated group include hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylate, and glycidyl (meth) acrylate.
アクリルウレタン系樹脂塗料には、光重合開始剤が含有される。光重合開始剤としては、アリールケトン系光重合開始剤、含イオウ系光重合開始剤、その他の光重合開始剤等が挙げられる。アリールケトン系光重合開始剤としては、例えばアセトフェノン類、ベンゾフェノン類、アルキルアミノベンゾフェノン類、ベンゾイルベンゾエート類、α−アシロキシムエステル類等が挙げられる。また含イオウ系光重合開始剤としては、例えばスルフィド類、チオキサントン類等が挙げられる。これらの光重合開始剤は２種以上を併用することができる。光重合開始剤は、アミン類等の光増感剤と組み合わせて使用することができる。光重合開始剤の割合は、塗料中の樹脂量（固形分換算量）に対し、０．５〜２０重量％が好ましい。 The acrylic urethane resin coating contains a photopolymerization initiator. Examples of the photopolymerization initiator include aryl ketone photopolymerization initiators, sulfur-containing photopolymerization initiators, and other photopolymerization initiators. Examples of the aryl ketone photopolymerization initiator include acetophenones, benzophenones, alkylaminobenzophenones, benzoylbenzoates, α-acyloxime esters, and the like. Examples of sulfur-containing photopolymerization initiators include sulfides and thioxanthones. Two or more of these photopolymerization initiators can be used in combination. The photopolymerization initiator can be used in combination with a photosensitizer such as amines. The ratio of the photopolymerization initiator is preferably 0.5 to 20% by weight with respect to the amount of resin in the paint (in terms of solid content).
アクリルウレタン系樹脂塗料を硬化させる紫外線源としては、キセノンランプ、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク灯、タングステンランプ等が使用できる。照射時間は、ブロック層の厚み、紫外線源の種類等の条件により適宜設定される。 A xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like can be used as an ultraviolet ray source for curing the acrylic urethane resin coating. The irradiation time is appropriately set depending on conditions such as the thickness of the block layer and the type of the ultraviolet light source.
ブロック層は、帯電防止剤を含有していることが好ましい。帯電防止剤としては、カーボンブラック、グラファイト、銀、酸化錫、酸化亜鉛等の無機系帯電防止剤；ポリオキシエチレンソルビタンモノステアレート等のソルビタン系帯電防止剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアリルエーテル等のエーテル系帯電防止剤；ポリオキシエチレンアルキルアミン、ポリオキシエチレンアミド等のアミン及びアミド系帯電防止剤；ポリオキシエチレン脂肪酸エステル等の脂肪酸エステル系帯電防止剤；アルキルリン酸エステル塩、アルキルアリルスルホン酸、ジアルキルリン酸エステル金属塩、ポリスチレンスルホン酸トリエタノールアミン塩等のアニオン系帯電防止剤；アルキルアミン誘導体、第４級アンモニウム塩、ポリアミン酸化エチレン付加体、イミダゾリン等のカチオン系帯電防止剤；イミダゾリン金属塩、ジアミン金属塩、アラニン金属塩等の両性帯電防止剤；モノグリセリド系帯電防止剤等の有機系帯電防止剤等が挙げられるが、本発明においては酸化亜鉛と五酸化アンチモンの複酸化物が好ましい。ブロック層中の帯電防止剤の割合は、３〜２０重量％であるが、帯電防止剤として酸化亜鉛と五酸化アンチモンの複酸化物を用いる場合、ブロック層中の割合は、５〜２０重量％が好ましい。帯電防止剤として酸化亜鉛と五酸化アンチモンの複酸化物をブロック層中に含有していると、帯電防止効果のみならず、基材層中のリン酸トリアリールイソプロピル化物と相乗的に作用して、塩化ビニル系樹脂シートの難燃性を更に向上することができる。 The block layer preferably contains an antistatic agent. Antistatic agents include inorganic antistatic agents such as carbon black, graphite, silver, tin oxide and zinc oxide; sorbitan antistatic agents such as polyoxyethylene sorbitan monostearate; polyoxyethylene alkyl ether, polyoxyethylene Ether-based antistatic agents such as allyl ether; amines such as polyoxyethylene alkylamines and polyoxyethylene amides and amide-based antistatic agents; fatty acid ester-based antistatic agents such as polyoxyethylene fatty acid esters; alkyl phosphate ester salts; Anionic antistatic agents such as alkylallyl sulfonic acid, dialkyl phosphoric acid ester metal salt, polystyrene sulfonic acid triethanolamine salt; alkylamine derivative, quaternary ammonium salt, polyamine ethylene oxide adduct, cation such as imidazoline Antistatic agents such as imidazoline metal salts, diamine metal salts, and alanine metal salts; organic antistatic agents such as monoglyceride antistatic agents and the like. In the present invention, zinc oxide and pentoxide Antimony double oxide is preferred. The proportion of the antistatic agent in the block layer is 3 to 20% by weight, but when a double oxide of zinc oxide and antimony pentoxide is used as the antistatic agent, the proportion in the block layer is 5 to 20% by weight. Is preferred. When a double oxide of zinc oxide and antimony pentoxide is contained in the block layer as an antistatic agent, it acts synergistically not only with the antistatic effect but also with triaryl isopropylate in the base material layer. The flame retardancy of the vinyl chloride resin sheet can be further improved.
本発明の塩化ビニル系樹脂シートは、テーブルシート、デスクシート等の被覆・保護用シート、工場等におけるパーティション用シート等として利用することができる。 The vinyl chloride resin sheet of the present invention can be used as a covering / protecting sheet such as a table sheet or a desk sheet, a partition sheet in a factory or the like.
以下、実施例、比較例を挙げて、本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例１〜９、比較例１〜５
表１に示す組成の塩化ビニル系樹脂組成物をカレンダー成形し、厚さ１．０ｍｍの基材層を形成した。この基材層の片面に表１に示す組成のアクリルウレタン系樹脂組成物を、乾燥後の厚みが２０μｍとなるようにコーティングし、高圧水銀灯を照射（積算光量３５０ｍJ／ｃｍ２）してブロック層を形成して塩化ビニル系樹脂シートとした。得られた塩化ビニル系樹脂シートの物性の評価を表１にあわせて示す。尚、表中の数値は「質量部」である。
Examples 1-9, Comparative Examples 1-5
A vinyl chloride resin composition having the composition shown in Table 1 was calendered to form a substrate layer having a thickness of 1.0 mm. One side of this base material layer is coated with an acrylic urethane resin composition having the composition shown in Table 1 so that the thickness after drying is 20 μm, and irradiated with a high-pressure mercury lamp (integrated light quantity 350 mJ / cm 2 ) to form a block layer To form a vinyl chloride resin sheet. Table 1 shows the evaluation of physical properties of the obtained vinyl chloride resin sheet. The numerical values in the table are “parts by mass”.
尚、基材層を形成するポリ塩化ビニル、塩化ビニル系樹脂組成物中の可塑剤、熱安定剤、リン酸エステル系化合物、無機系難燃剤としては以下のものを用いた。 In addition, the following were used as the polyvinyl chloride which forms a base material layer, the plasticizer in a vinyl chloride resin composition, a heat stabilizer, a phosphate ester compound, and an inorganic flame retardant.
ポリ塩化ビニル：重合度１０００
可塑剤：フタル酸ジオクチルエステル
熱安定剤１：エポキシ化大豆油
リン酸エステル系化合物１：リン酸トリアリールプロピル（粘度４４ｍｍ２／ｓ、２５℃）
リン酸エステル系化合物２：トリクレジルホスフェート
リン酸エステル系化合物３：ｔ−ブチルフェニルジフェニルホスフェート
無機系難燃剤：水酸化アルミニウム
Polyvinyl chloride: degree of polymerization 1000
Plasticizer: Dioctyl phthalate thermal stabilizer 1: Epoxidized soybean oil phosphate ester compound 1: Triarylpropyl phosphate (viscosity 44 mm 2 / s, 25 ° C.)
Phosphate ester compound 2: tricresyl phosphate phosphate ester compound 3: t-butylphenyl diphenyl phosphate inorganic flame retardant: aluminum hydroxide
また、アクリルウレタン系樹脂及び、アクリルウレタン系樹脂組成物中の帯電防止剤としては以下のものを用いた。
アクリルウレタン系樹脂：ヘンケルジャパン社製 ＵＶＣ−Ｂ１
帯電防止剤１：酸化亜鉛と五酸化アンチモンの複酸化物
帯電防止剤２：ポリオキシエチレンアルキルエーテル
帯電防止剤３：カーボンブラック
Moreover, the following were used as an antistatic agent in acrylic urethane type resin and acrylic urethane type resin composition.
Acrylic urethane resin: Henkel Japan UVC-B1
Antistatic agent 1: Double oxide antistatic agent of zinc oxide and antimony pentoxide 2: Polyoxyethylene alkyl ether antistatic agent 3: Carbon black
※１ 難燃性
消防法告示の防炎性能試験４５°ミクロバーナー法に準拠して測定し、以下の基準で評価した。
◎・・・残炎時間が３秒未満。
○・・・残炎時間が３秒以上、５秒以下。
×・・・残炎時間が５秒を超える。
* 1 Flame retardancy Measured in accordance with the 45 ° micro burner method of the flameproof performance test published by the Fire Service Law, and evaluated according to the following criteria.
◎ ・ ・ ・ After flame time is less than 3 seconds.
○: After flame time is 3 seconds or more and 5 seconds or less.
X: The afterflame time exceeds 5 seconds.
※２ 透明性
ＪＩＳ−Ｋ７１０５に基づき、ヘイズ値を測定し、以下の基準で評価した。
○・・・ヘイズ値が１０％以下。
×・・・ヘイズ値が１０％を超える。
* 2 Transparency Haze value was measured based on JIS-K7105 and evaluated according to the following criteria.
○: Haze value is 10% or less.
X: The haze value exceeds 10%.
※３ ブリード性
成形から２週間後の塩化ビニル系樹脂シートについて、シート表面を布で拭き取り、布面への付着物の有無を確認し、以下の基準で評価した。
○・・・付着物なし。
×・・・付着物あり。
* 3 Bleed property For the vinyl chloride resin sheet two weeks after molding, the surface of the sheet was wiped with a cloth, the presence or absence of deposits on the cloth surface was confirmed, and the following criteria were evaluated.
○: No deposits.
X: There are deposits.
※４ 臭気
シートの成形加工中におけるリン酸エステル系化合物に起因する臭気の有無を確認し、以下の基準で評価した。
○・・・臭気はない。
△・・・若干臭気がある。
×・・・臭気がある。
* 4 Odor The presence or absence of odor caused by phosphate ester compounds during sheet forming was confirmed and evaluated according to the following criteria.
○ ・ ・ ・ No odor.
Δ: Some odor.
X: There is an odor.
※５ 電気特性
印加電圧１０００Ｖにおける抵抗値を測定し、以下の基準で電気特性の有無を評価した。
有・・・Ｅ＋１０以下。
無・・・Ｅ＋１０を超える。
* 5 Electrical characteristics The resistance value at an applied voltage of 1000 V was measured, and the presence or absence of electrical characteristics was evaluated according to the following criteria.
Existence: E + 10 or less.
No ... Exceeds E + 10.
Claims (2)
ブロック層には酸化亜鉛と五酸化アンチモンの複酸化物である帯電防止剤が含有されていることを特徴とする塩化ビニル系樹脂シート。 It consists of a base material layer and a block layer provided on at least one side of the base material layer. The base material layer is made of a vinyl chloride resin containing a plasticizer and a triaryl isopropylated product, and the block layer is an acrylic urethane. Ri name from the system resin,
Vinyl chloride resin sheet in the block layer, wherein Rukoto antistatic agent is a mixed oxide of zinc oxide and antimony pentoxide is contained.
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| GB2027712B (en) * | 1978-07-21 | 1983-03-23 | Ciba Geigy Ag | Triary phosphates |
| GB8624082D0 (en) * | 1986-10-08 | 1986-11-12 | Dunlop Cct Sa | Vinyl chloride polymer products |
| JPH115882A (en) * | 1997-06-19 | 1999-01-12 | Mitsui Chem Inc | Vinyl chloride resin composition for molding |
| US8143433B2 (en) * | 2006-04-24 | 2012-03-27 | Albemarle Corporation | Low triphenylphosphate, high phosphorous content isopropyl phenyl phosphates with high ortho alkylation |
| JP5255866B2 (en) * | 2008-02-29 | 2013-08-07 | アキレス株式会社 | Vinyl chloride resin sheet for desk mats or table mats |
| AU2009288142B2 (en) * | 2008-09-02 | 2016-04-21 | Interface, Inc. | Low weight carpet and carpet tile and methods of manufacture, sizing and installation |
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| JP5729552B2 (en) * | 2011-03-23 | 2015-06-03 | 日本ゼオン株式会社 | Vinyl chloride resin composition for powder molding, vinyl chloride resin molded body and laminate |
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