JP6569299B2 - Resin composition, resin sheet, laminated sheet and foamed wallpaper - Google Patents
Resin composition, resin sheet, laminated sheet and foamed wallpaper Download PDFInfo
- Publication number
- JP6569299B2 JP6569299B2 JP2015105580A JP2015105580A JP6569299B2 JP 6569299 B2 JP6569299 B2 JP 6569299B2 JP 2015105580 A JP2015105580 A JP 2015105580A JP 2015105580 A JP2015105580 A JP 2015105580A JP 6569299 B2 JP6569299 B2 JP 6569299B2
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- Prior art keywords
- resin
- foaming
- resin composition
- base material
- foamed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 title claims description 115
- 239000011347 resin Substances 0.000 title claims description 115
- 239000011342 resin composition Substances 0.000 title claims description 39
- 238000005187 foaming Methods 0.000 claims description 52
- 239000004088 foaming agent Substances 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 40
- 150000005846 sugar alcohols Polymers 0.000 claims description 32
- 239000006260 foam Substances 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 11
- 229920001684 low density polyethylene Polymers 0.000 claims description 10
- 239000004702 low-density polyethylene Substances 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 9
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- FRZSCIVUSFMNBX-UHFFFAOYSA-L zinc;12-hydroxyoctadecanoate Chemical compound [Zn+2].CCCCCCC(O)CCCCCCCCCCC([O-])=O.CCCCCCC(O)CCCCCCCCCCC([O-])=O FRZSCIVUSFMNBX-UHFFFAOYSA-L 0.000 claims description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
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- 235000011076 sorbitan monostearate Nutrition 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 43
- 239000000194 fatty acid Substances 0.000 description 43
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- 150000004665 fatty acids Chemical class 0.000 description 43
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- 239000002184 metal Substances 0.000 description 38
- 150000003839 salts Chemical class 0.000 description 36
- 125000000524 functional group Chemical group 0.000 description 32
- 238000000034 method Methods 0.000 description 31
- 239000010410 layer Substances 0.000 description 29
- -1 polytetrafluoroethylene Polymers 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 239000000976 ink Substances 0.000 description 15
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 238000000465 moulding Methods 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- 230000007423 decrease Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 10
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
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- 238000004519 manufacturing process Methods 0.000 description 8
- 238000007639 printing Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
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- 238000010894 electron beam technology Methods 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
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- 239000002253 acid Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
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- 239000004156 Azodicarbonamide Substances 0.000 description 5
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- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 5
- 235000019399 azodicarbonamide Nutrition 0.000 description 5
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- 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 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- 229920003355 Novatec® Polymers 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
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- 238000006731 degradation reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
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- 239000007788 liquid Substances 0.000 description 3
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
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- 239000000758 substrate Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 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 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
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- 230000009878 intermolecular interaction Effects 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
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- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- HPBJPFJVNDHMEG-UHFFFAOYSA-L magnesium;octanoate Chemical compound [Mg+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HPBJPFJVNDHMEG-UHFFFAOYSA-L 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- ULQHHSKTTGCVLP-UHFFFAOYSA-L zinc;2-hydroxydodecanoate Chemical group [Zn+2].CCCCCCCCCCC(O)C([O-])=O.CCCCCCCCCCC(O)C([O-])=O ULQHHSKTTGCVLP-UHFFFAOYSA-L 0.000 description 1
- NPJHXSZKSBSLLK-UHFFFAOYSA-L zinc;2-hydroxyoctadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCC(O)C([O-])=O.CCCCCCCCCCCCCCCCC(O)C([O-])=O NPJHXSZKSBSLLK-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Description
本発明は、樹脂組成物、樹脂シート、積層シート及び発泡壁紙に関する。より詳細には、本発明は、戸建て住宅、集合住宅、店舗、事務所ビル等の建築物の壁面装飾などに利用可能な発泡壁紙並びにそれに用いられる樹脂組成物、樹脂シート及び積層シートに関する。 The present invention relates to a resin composition, a resin sheet, a laminated sheet, and foamed wallpaper. More specifically, the present invention relates to a foam wallpaper that can be used for decorating a wall of a building such as a detached house, an apartment house, a store, or an office building, and a resin composition, resin sheet, and laminated sheet used therefor.
建築物の壁面装飾等に用いる壁紙としては、紙基材に塩化ビニル樹脂の樹脂層を設けた塩化ビニル壁紙が広く利用されている。近年、環境に配慮し、エチレン−酢酸ビニル共重合体のようなハロゲンを含有しない樹脂が用いられてきている（例えば、下記特許文献１及び２を参照）。 As wallpaper used for wall decoration of buildings, etc., vinyl chloride wallpaper in which a resin layer of vinyl chloride resin is provided on a paper base material is widely used. In recent years, in consideration of the environment, a halogen-free resin such as an ethylene-vinyl acetate copolymer has been used (for example, see Patent Documents 1 and 2 below).
これらの発泡壁紙の製造方法として、基材上に、発泡剤が含まれる樹脂組成物を溶融押出コートし積層するか、別途Ｔダイ押出法によりシーティングしておき、後からドライラミネート又は熱ラミネートにて基材を貼り合わせるかして、基材上に樹脂シートが設けられた積層シートを得た後、必要に応じて表面に印刷が施された樹脂シートを加熱して発泡剤を分解・発泡させる方法がある。 As a method for producing such foamed wallpaper, a resin composition containing a foaming agent is melt-extruded and laminated on a base material, or is separately sheeted by a T-die extrusion method, and later applied to dry lamination or heat lamination. After laminating the base material to obtain a laminated sheet with a resin sheet provided on the base material, the resin sheet with the surface printed thereon is heated as necessary to decompose and foam the foaming agent. There is a way to make it.
このような熱分解型の発泡剤を添加するタイプの発泡壁紙では、発泡剤の分解促進や分解温度の調整等を目的として、脂肪酸金属塩を発泡助剤として用いることが知られている。例えば、特許文献３では、ステアリン酸亜鉛及びオクチル酸亜鉛を発泡助剤として用いることが開示されている。 In foamed wallpaper of a type to which such a thermal decomposition type foaming agent is added, it is known that a fatty acid metal salt is used as a foaming aid for the purpose of accelerating the decomposition of the foaming agent and adjusting the decomposition temperature. For example, Patent Document 3 discloses that zinc stearate and zinc octylate are used as foaming aids.
ところで、発泡壁紙には加飾のために表面に印刷層を設けることが一般的である。しかし、上述した脂肪酸金属塩を、高い発泡倍率が得られるように配合した発泡壁紙用の樹脂シートは、表面に印刷を施すような製品に用いる場合、インキの密着性、絵柄模様の転移性等の印刷適性が低下することがあった。 By the way, it is common to provide a printing layer on the surface of the foam wallpaper for decoration. However, the resin sheet for foamed wallpaper in which the above-mentioned fatty acid metal salt is blended so as to obtain a high foaming ratio is used when the product is printed on the surface. The printability of the ink sometimes deteriorated.
上記のような問題に対し、本発明者らは、炭素鎖に官能基を鵜ゆする脂肪酸金属塩を使用することでこのブリードアウトによる密着性低下を効果的に抑えられることを見出している。しかし、本発明者らはさらなる検討の結果、特定の官能基を選択したときの壁紙の発泡過程において樹脂が変色する場合があることも判明している。 In response to the above problems, the present inventors have found that the use of a fatty acid metal salt having a functional group in the carbon chain can effectively suppress the decrease in adhesion due to the bleed out. However, as a result of further studies, the present inventors have also found that the resin may change color during the foaming process of wallpaper when a specific functional group is selected.
本発明は、上記事情に鑑みてなされたものであり、良好な発泡性を有し且つ十分な印刷適性を有するとともに発泡過程での変色が発生しにくい樹脂組成物、樹脂シート、積層シート及び発泡壁紙を提供することを目的とする。 The present invention has been made in view of the above circumstances, and has a resin composition, a resin sheet, a laminated sheet, and a foam having good foamability and sufficient printability and hardly causing discoloration in the foaming process. The purpose is to provide wallpaper.
すなわち、本発明は、基材と、該基材上に設けられた発泡樹脂層と、を備える発泡壁紙の発泡樹脂層を形成するための樹脂組成物であって、充填剤と、発泡剤と、発泡助剤と、樹脂分と、多価アルコールと、を含み、発泡助剤が、脂肪酸金属塩の炭素鎖に活性プロトンを含む官能基を有する官能基含有脂肪酸金属塩を含む、樹脂組成物を提供する。 That is, the present invention is a resin composition for forming a foamed resin layer of a foam wallpaper comprising a base material and a foamed resin layer provided on the base material, the filler, the foaming agent, A resin composition comprising a foaming aid, a resin component, and a polyhydric alcohol, wherein the foaming aid comprises a functional group-containing fatty acid metal salt having a functional group containing an active proton in the carbon chain of the fatty acid metal salt. I will provide a.
本発明の樹脂組成物によれば、良好な発泡性を有し且つ十分な印刷適性を有するとともに発泡過程での変色が発生しにくい樹脂シートを形成することができる。このような効果が得られる理由を、本発明者らは以下のように推察する。 According to the resin composition of the present invention, it is possible to form a resin sheet that has good foamability and sufficient printability and is unlikely to cause discoloration during the foaming process. The present inventors infer the reason why such an effect is obtained as follows.
まず、従来の脂肪酸金属塩が配合された樹脂シートの印刷適性が低下する要因として、脂肪酸金属塩の界面活性作用が非常に強く、印刷が施される表面又は印刷後の印刷界面にブリードアウトした脂肪酸金属塩が、表面の濡れ性や親インク性を低下させたり、インキの密着性を低下させたりすることが考えられる。これに対し、本発明では、上記官能基含有脂肪酸金属塩を発泡助剤として用いることで、良好な発泡性を得つつ、脂肪酸金属塩の炭素鎖に付加している活性プロトンを含む官能基が周囲の樹脂と相互作用し、印刷が施される表面又は印刷後の印刷界面へのブリードアウトを低減することができるため、印刷適性が維持されたものと本発明者らは考えている。 First, as a factor that decreases the printability of a resin sheet containing a conventional fatty acid metal salt, the surfactant activity of the fatty acid metal salt is very strong, and bleeds out to the surface on which printing is performed or the printing interface after printing. It is conceivable that the fatty acid metal salt decreases the wettability of the surface and the ink affinity, or decreases the adhesion of the ink. On the other hand, in the present invention, by using the functional group-containing fatty acid metal salt as a foaming aid, a functional group containing an active proton added to the carbon chain of the fatty acid metal salt is obtained while obtaining good foamability. The present inventors consider that the printability is maintained because the bleed-out to the surface on which printing is performed or the printing interface after printing can be reduced by interacting with the surrounding resin.
一方、上述したとおり本発明者らは上記官能基含有脂肪酸金属塩を発泡助剤として用いる場合、得られる発泡壁紙が変色する場合があることを見出している。これは、系中の活性プロトンが発泡剤と相互作用することで分解過程が変化し、呈色物質が発生することによるものと考えられる。これに対し、本発明では、多価アルコールを用いることで、発泡剤と相互作用する活性プロトンを多価アルコールと水素結合させ、呈色物質の生成を抑え、得られる発泡壁紙の変色を抑制することができたものと本発明者らは考えている。 On the other hand, as described above, the present inventors have found that when the functional group-containing fatty acid metal salt is used as a foaming aid, the resulting foamed wallpaper may be discolored. This is considered to be due to the fact that the active protons in the system interact with the foaming agent to change the decomposition process and generate a colored substance. On the other hand, in the present invention, by using a polyhydric alcohol, active protons that interact with the foaming agent are hydrogen-bonded with the polyhydric alcohol, thereby suppressing the generation of a colored substance and suppressing discoloration of the resulting foamed wallpaper. The present inventors consider that it was possible.
ところで、近年、消費者の化学物質に対する意識の高まりから、住宅に使われる発泡壁紙の印刷層には水系のインキが使用されている。しかしながら、これら水系のインキは樹脂に対する親和性の低さから密着性を確保しにくい。上記従来の脂肪酸金属塩は強い界面活性効果を持っているために、発泡壁紙表面へのブリードアウトが生じてしまった場合にはそのインキ密着性を著しく低下させることがあった。 By the way, in recent years, water-based inks have been used for printed layers of foamed wallpaper used in houses due to increasing consumer awareness of chemical substances. However, these water-based inks are difficult to ensure adhesion because of their low affinity for resins. Since the conventional fatty acid metal salt has a strong surface-active effect, when the bleed-out occurs on the surface of the foam wallpaper, the ink adhesion may be remarkably lowered.
これに対し、本発明の樹脂組成物によれば、発泡壁紙表面へのブリードアウトが生じにくいことから、水系のインキであってもインキ密着性を十分確保することが可能である。 On the other hand, according to the resin composition of the present invention, bleeding out to the surface of the foamed wallpaper is unlikely to occur, so that sufficient ink adhesion can be ensured even with water-based ink.
また、本発明の樹脂組成物によれば、例えば、積層シートの表面に非発泡層を設けて発泡助剤のブリードアウトをブロックする等といった処置を必要とせずとも十分な印刷適性を確保することができるので、より簡便なシート構造で十分な印刷適性と良好な発泡性とを兼ね備える樹脂シートを形成することができる。 In addition, according to the resin composition of the present invention, for example, a sufficient non-foaming layer is provided on the surface of the laminated sheet to ensure sufficient printability without requiring treatment such as blocking the bleeding out of the foaming aid. Therefore, a resin sheet having both sufficient printability and good foamability can be formed with a simpler sheet structure.
上記多価アルコールの含有量は、樹脂分１００質量部に対して０．１〜１５質量部であることが好ましい。多価アルコールの含有量を上記範囲とすることにより、多価アルコールによるブリードアウトを制限しながら発泡工程での呈色物質の発生をより効率的に抑えることができる。 It is preferable that content of the said polyhydric alcohol is 0.1-15 mass parts with respect to 100 mass parts of resin parts. By setting the content of the polyhydric alcohol in the above range, it is possible to more efficiently suppress the generation of the colored substance in the foaming process while restricting the bleed out due to the polyhydric alcohol.
上記多価アルコールの含有量は、官能基含有脂肪酸金属塩１００質量部に対して３０〜２００質量部であることが好ましい。多価アルコールの含有量を上記範囲とすることにより、多価アルコールによるブリードアウトを制限しながら発泡工程での呈色物質の発生をより効率的に抑えることができ、印刷適性も良好に保つことができる。多価アルコールの含有量が官能基含有脂肪酸金属塩１００質量部に対して３０質量部以上であれば、呈色抑制効果が得られやすくなり、２００質量部以下であれば、多価アルコールによるブリードアウトを制限することができる。 It is preferable that content of the said polyhydric alcohol is 30-200 mass parts with respect to 100 mass parts of functional group containing fatty acid metal salt. By making the content of the polyhydric alcohol within the above range, it is possible to more efficiently suppress the generation of colored substances in the foaming process while limiting the bleed-out due to the polyhydric alcohol, and to maintain good printability. Can do. If the content of the polyhydric alcohol is 30 parts by mass or more with respect to 100 parts by mass of the functional group-containing fatty acid metal salt, a coloration suppressing effect is easily obtained. You can limit out.
上記官能基は、水酸基であることが好ましい。脂肪酸金属塩の炭素鎖に水酸基を有する水酸基含有脂肪酸金属塩を用いることで、樹脂組成物の発泡性及び印刷適性を高水準で両立させると同時に発泡工程での呈色物質の発生をより効率的に抑えることができる。このような効果が得られる理由として、水酸基は、活性プロトンを有する官能基としては酸解離定数が低いため、系中の活性プロトン濃度が抑えられることで呈色物質の発生をより抑えることができ、なおかつ炭素−水素結合に比べて強い分極に起因する電気的な分子間相互作用がより強固に働き、より効果的にブリードアウトが低減できることが考えられる。 The functional group is preferably a hydroxyl group. By using a hydroxyl group-containing fatty acid metal salt having a hydroxyl group in the carbon chain of the fatty acid metal salt, the foamability and printability of the resin composition are compatible at a high level, and at the same time, the generation of colored substances in the foaming process is more efficient. Can be suppressed. The reason why such an effect can be obtained is that, since a hydroxyl group has a low acid dissociation constant as a functional group having an active proton, generation of a colored substance can be further suppressed by suppressing the active proton concentration in the system. In addition, it is conceivable that the electrical intermolecular interaction resulting from the strong polarization as compared with the carbon-hydrogen bond works more strongly and bleed out can be reduced more effectively.
上記樹脂分は、密度０．９１ｇ／ｃｍ３以上０．９４ｇ／ｃｍ３以下の低密度ポリエチレンを少なくとも含むことが好ましい。このような樹脂分を用いることにより、樹脂の柔軟性を向上させることができ、良好な発泡状態の発泡樹脂層を有し、施工性にも優れた発泡壁紙を実現することが容易となる。 The resin component preferably contains at least a density of 0.91 g / cm 3 or more 0.94 g / cm 3 or less of low density polyethylene. By using such a resin component, the flexibility of the resin can be improved, and it becomes easy to realize a foamed wallpaper having a foamed resin layer in a good foamed state and excellent in workability.
上記樹脂分は、上述した低密度ポリエチレンに加えて、密度０．８８ｇ／ｃｍ３以上０．９１ｇ／ｃｍ３未満の超低密度ポリエチレンを更に含むことが好ましい。このような樹脂分を用いることにより、樹脂の柔軟性を更に向上させることができ、良好な発泡状態の発泡樹脂層を有し、施工性にも優れた発泡壁紙を実現することがより容易となる。 The resin component, in addition to the low density polyethylene described above, may further include an ultra low density polyethylene density of less than 0.88 g / cm 3 or more 0.91 g / cm 3. By using such a resin component, the flexibility of the resin can be further improved, and it is easier to realize a foamed wallpaper having a foamed resin layer in a good foamed state and excellent in workability. Become.
また、本発明は、上記本発明に係る樹脂組成物を押出製膜して得られる樹脂シートを提供する。この樹脂シートは、架橋処理が施されていてもよい。これにより、発泡時のガス抜けを抑制することができ、均一且つ表面からのガス抜けが少ない発泡樹脂層を得ることができる。 The present invention also provides a resin sheet obtained by extrusion film formation of the resin composition according to the present invention. This resin sheet may be subjected to a crosslinking treatment. Thereby, the gas escape at the time of foaming can be suppressed, and the foamed resin layer with little gas escape from the surface can be obtained.
また、本発明は、基材と、該基材上に設けられた、上記本発明に係る樹脂シートとを備える積層シートを提供する。 Moreover, this invention provides a laminated sheet provided with the base material and the resin sheet which concerns on the said this invention provided on this base material.
本発明はまた、基材と、該基材上に設けられた発泡樹脂層と、を備える発泡壁紙であって、上記本発明に係る積層シートにおける上記樹脂シートに含まれる発泡剤を発泡させて得られる発泡壁紙を提供する。 The present invention is also a foam wallpaper comprising a base material and a foamed resin layer provided on the base material, wherein the foaming agent contained in the resin sheet in the laminated sheet according to the present invention is foamed. The resulting foamed wallpaper is provided.
本発明によれば、良好な発泡性を有し且つ十分な印刷適性を有するとともに発泡過程での変色が発生しにくい樹脂組成物、樹脂シート、積層シート及び発泡壁紙を提供することができる。 According to the present invention, it is possible to provide a resin composition, a resin sheet, a laminated sheet, and a foamed wallpaper that have good foamability and sufficient printability and are less likely to be discolored during the foaming process.
［樹脂組成物］
本実施形態に係る樹脂組成物は、基材と、該基材上に設けられた発泡樹脂層と、を備える発泡壁紙の発泡樹脂層を形成するための樹脂組成物であって、充填剤と、発泡剤と、発泡助剤と、樹脂分と、多価アルコールと、を含む。
[Resin composition]
The resin composition according to the present embodiment is a resin composition for forming a foamed resin layer of a foamed wallpaper comprising a base material and a foamed resin layer provided on the base material, and a filler, , A foaming agent, a foaming aid, a resin component, and a polyhydric alcohol.
本実施形態における充填剤としては、無機充填剤及び有機充填剤が挙げられる。無機充填剤としては、例えば、炭酸カルシウム、二酸化チタン等が挙げられる。有機充填剤としては、例えば、メラミンシアヌレート、ポリテトラフルオロエチレン（ＰＴＦＥ）、木粉、セルロース及びその誘導体が挙げられる。これらの充填剤は１種を単独で、又は２種以上を併用して用いることができる。 Examples of the filler in the present embodiment include inorganic fillers and organic fillers. Examples of the inorganic filler include calcium carbonate and titanium dioxide. Examples of the organic filler include melamine cyanurate, polytetrafluoroethylene (PTFE), wood flour, cellulose and derivatives thereof. These fillers can be used alone or in combination of two or more.
充填剤の含有量は、特に制限されないが、その合計量が、樹脂組成物全量を基準として１０〜６０質量％であることが好ましい。充填剤を添加する理由としては、発泡壁紙の隠蔽性の確保、単位面積当たりの燃焼カロリーの低減、嵩増しによる製造コストの低減等が挙げられる。充填剤（特には無機充填剤）の含有量が樹脂組成物全量を基準として２０〜４０質量％であると、発泡壁紙としての良好な隠蔽性を確保しながら燃焼カロリーが低い発泡壁紙を低製造コストで製造することができる。 The content of the filler is not particularly limited, but the total amount is preferably 10 to 60% by mass based on the total amount of the resin composition. Reasons for adding the filler include securing the concealment property of the foam wallpaper, reducing the calorie burn per unit area, and reducing the production cost due to the increase in volume. When the content of the filler (especially inorganic filler) is 20 to 40% by mass based on the total amount of the resin composition, low production of foam wallpaper with low combustion calories while ensuring good concealment as a foam wallpaper. Can be manufactured at cost.
充填剤としては、例えば、ソフトン１０００（備北粉化株式会社製、炭酸カルシウム）、タイペークＣＲ−６０−２（石原産業株式会社製、二酸化チタン）等の市販品を用いることができる。 As the filler, for example, commercially available products such as Softon 1000 (Calcium Carbonate, manufactured by Bihoku Powder Co., Ltd.), and Taipei CR-60-2 (Titanium Dioxide, manufactured by Ishihara Sangyo Co., Ltd.) can be used.
本実施形態に係る発泡剤としては、例えば、熱分解型発泡剤を用いることができる。熱分解型発泡剤としては、例えば、アゾジカルボンアミド（ＡＤＣＡ）、アゾブチロニトリル、ジアゾアミノベンゼン等のアゾ系発泡剤、ｐ−トルエンスルホニルヒドラジド等のヒドラジド系発泡剤、Ｎ，Ｎ’−ジニトロソペンタメチレンテトラミン等のニトロソ系発泡剤などが挙げられる。これらの中でも、毒性が少なく、発泡開始温度の調節が容易で適用範囲の広いＡＤＣＡが好ましい。これらは１種を単独で、又は２種以上を併用して用いることができる。 As the foaming agent according to the present embodiment, for example, a pyrolytic foaming agent can be used. Examples of the pyrolytic foaming agent include azo foaming agents such as azodicarbonamide (ADCA), azobutyronitrile, and diazoaminobenzene, hydrazide foaming agents such as p-toluenesulfonyl hydrazide, and N, N′-di. Examples thereof include nitroso-based foaming agents such as nitrosopentamethylenetetramine. Among these, ADCA is preferable because it has little toxicity, easily adjusts the foaming start temperature, and has a wide application range. These can be used alone or in combination of two or more.
発泡剤としては、例えば、ビニホールＡＣ＃３Ｃ−Ｋ２（永和化成株式会社製、アゾジカルボンアミド系発泡剤）、セルラーＤ（永和化成株式会社製、ニトロソ系発泡剤）、ネオセルボン ＳＢ＃５１（永和化成株式会社製、ヒドラジド系発泡剤）等の市販品を用いることができる。 Examples of the foaming agent include VINYHALL AC # 3C-K2 (manufactured by Eiwa Kasei Co., Ltd., azodicarbonamide-based foaming agent), Cellular D (manufactured by Eiwa Kasei Co., Ltd., nitroso-based foaming agent), Neoselbon SB # 51 (Yewa Kasei). Commercial products such as a hydrazide-based foaming agent (manufactured by Co., Ltd.) can be used.
発泡剤の含有量は、特に制限されないが、その合計量が、樹脂組成物全量を基準として１〜２０質量％であることが好ましい。発泡剤の含有量が上記範囲であると、過剰なガスの発生による表面からのガス抜けが抑制されている発泡樹脂層を得ることができる。 Although content of a foaming agent is not restrict | limited in particular, It is preferable that the total amount is 1-20 mass% on the basis of the resin composition whole quantity. When the content of the foaming agent is within the above range, it is possible to obtain a foamed resin layer in which gas escape from the surface due to generation of excessive gas is suppressed.
本実施形態に係る発泡助剤は、脂肪酸金属塩の炭素鎖に活性プロトンを含む官能基を有する官能基含有脂肪酸金属塩を含む。ここで、脂肪酸金属塩の炭素鎖とは、脂肪酸を構成する直鎖状の炭化水素基を指す。直鎖状の炭化水素基は、飽和であっても不飽和であってもよく、その炭素数は６〜３０が好ましいが、炭素数が少なくなると金属石鹸（脂肪酸金属塩）の融点が低下して液状になり取り扱いが難しくなるという点や、あまり炭素鎖が長すぎると融点が高くなりすぎて成型温度での分解性が低下するという観点から、炭素数は１０〜２４がより好ましい。このような炭化水素基を有する脂肪酸としては、例えば、ヘキサン酸、ステアリン酸、ラウリン酸、ベヘン酸等の飽和脂肪酸系、セバシン酸、アゼライン酸等のジカルボン酸系、オレイン酸、リノール酸、ウンデシレン酸等の不飽和カルボン酸系などが挙げられる。 The foaming auxiliary agent according to this embodiment includes a functional group-containing fatty acid metal salt having a functional group containing an active proton in the carbon chain of the fatty acid metal salt. Here, the carbon chain of the fatty acid metal salt refers to a linear hydrocarbon group constituting the fatty acid. The linear hydrocarbon group may be saturated or unsaturated, and preferably has 6 to 30 carbon atoms. However, when the number of carbon atoms decreases, the melting point of the metal soap (fatty acid metal salt) decreases. The number of carbon atoms is more preferably 10 to 24 from the viewpoint that it becomes liquid and difficult to handle, and that if the carbon chain is too long, the melting point becomes too high and the decomposability at the molding temperature decreases. Examples of fatty acids having such a hydrocarbon group include saturated fatty acids such as hexanoic acid, stearic acid, lauric acid, and behenic acid, dicarboxylic acids such as sebacic acid and azelaic acid, oleic acid, linoleic acid, and undecylenic acid. And the like, and the like.
ここで、活性プロトンを含む官能基とは、上記直鎖状の炭化水素基に直接結合する有機基のうち、２５℃の水中での酸解離定数が１８以下であるものが挙げられる。酸解離定数の下限値については特に制限されないが、樹脂分の酸劣化、充填剤の凝集・酸変性、及び壁紙としての一般使用の観点から、９以上であってもよい。同一分子中における上記官能基の個数については特に制限されず、官能基を２個以上有する場合には、これらは互いに同一でも異なっていてもよい。 Here, the functional group containing an active proton includes those having an acid dissociation constant of 18 or less in water at 25 ° C. among organic groups directly bonded to the linear hydrocarbon group. The lower limit of the acid dissociation constant is not particularly limited, but may be 9 or more from the viewpoint of acid degradation of the resin, aggregation / acid modification of the filler, and general use as wallpaper. The number of the functional groups in the same molecule is not particularly limited, and when two or more functional groups are present, these may be the same or different.
上記官能基としては、例えば、水酸基、ニトロメチル基、メルカプト基等が挙げられる。中でも、官能基は入手の容易な水酸基であることが好ましい。水酸基含有脂肪酸金属塩を用いることで、水酸基の強い分極に起因する電気的な分子間相互作用がより強固に働き、より効果的にブリードアウトが低減され、発泡性と印刷適性とを更に高水準で両立することができる。特に、樹脂分としてエチレン単独重合体又はエチレンと他のオレフィンとの共重合体と組み合わせた場合には、ベース樹脂の表面エネルギーの差があるためにブリードアウトの低減による親インク性の向上効果がより大きく発揮され、印刷適性の良好な壁紙用原反としての樹脂シートや積層シートを得ることができる。さらに、水酸基は、活性プロトンを有する官能基としては酸解離定数が低いため、系中の活性プロトン濃度が抑えられることで呈色物質の発生をより抑えることができる。 Examples of the functional group include a hydroxyl group, a nitromethyl group, a mercapto group, and the like. Among these, the functional group is preferably a readily available hydroxyl group. By using a hydroxyl group-containing fatty acid metal salt, electrical intermolecular interaction due to strong polarization of the hydroxyl group works more strongly, bleedout is reduced more effectively, and foamability and printability are further improved. Can be compatible. In particular, when combined with an ethylene homopolymer or a copolymer of ethylene and another olefin as the resin component, there is a difference in the surface energy of the base resin, so there is an effect of improving ink affinity by reducing bleed out. It is possible to obtain a resin sheet or a laminated sheet as a wallpaper material that is more greatly exhibited and has good printability. Furthermore, since a hydroxyl group has a low acid dissociation constant as a functional group having an active proton, generation of a colored substance can be further suppressed by suppressing the active proton concentration in the system.
官能基含有脂肪酸金属塩の官能基含有脂肪酸としては、例えば、ヒドロキシラウリン酸、ヒドロキシステアリン酸、リシノール酸、ジヒドロキシステアリン酸、ジヒドロキシラウリン酸等が挙げられる。 Examples of the functional group-containing fatty acid of the functional group-containing fatty acid metal salt include hydroxylauric acid, hydroxystearic acid, ricinoleic acid, dihydroxystearic acid, dihydroxylauric acid, and the like.
官能基含有脂肪酸金属塩の金属としては、例えば、バリウム、マグネシウム、カルシウム、亜鉛等が挙げられるが、中でも亜鉛である場合は、発泡助剤としての活性が非常に強く、特に有用である。 Examples of the metal of the functional group-containing fatty acid metal salt include barium, magnesium, calcium, zinc, and the like. Among them, zinc is particularly useful because it has very strong activity as a foaming aid.
本実施形態に係る官能基含有脂肪酸金属塩は、上述した観点から、ヒドロキシラウリン酸亜鉛塩、ヒドロキシステアリン酸亜鉛塩、ジヒドロキシステアリン酸亜鉛塩、ジヒドロキシラウリン酸亜鉛塩が好ましいが、入手の容易さやコストの観点から、１２−ヒドロキシステアリン酸亜鉛がより好ましい。また、これら官能基含有脂肪酸金属塩は、１種を単独で、又は２種以上を併用して用いることができる。 The functional group-containing fatty acid metal salt according to the present embodiment is preferably a hydroxylauric acid zinc salt, a hydroxystearic acid zinc salt, a dihydroxystearic acid zinc salt, or a dihydroxylauric acid zinc salt from the viewpoints described above. From this point of view, zinc 12-hydroxystearate is more preferable. Moreover, these functional group containing fatty acid metal salts can be used individually by 1 type or in combination of 2 or more types.
本実施形態に係る官能基含有脂肪酸金属塩の含有量としては、樹脂分１００質量部に対して、１〜１０質量部の範囲内であることが好ましく、１〜８質量部の範囲内であることがより好ましい。当該含有量が樹脂分１００質量部に対して１〜１０質量部の範囲内であれば、より良好な印刷適性をもつ樹脂組成物を得ることができる。上記含有量が１質量部未満であると、官能基含有脂肪酸金属塩の発泡助剤としての効果が十分に得られにくく、発泡剤の分解効率が低下する傾向があり、１０質量部より多いと、製膜した樹脂シートの表面に存在する官能基含有脂肪酸金属塩の影響により、印刷適性が低下する傾向がある。 As content of the functional group containing fatty acid metal salt which concerns on this embodiment, it is preferable to exist in the range of 1-10 mass parts with respect to 100 mass parts of resin parts, and it exists in the range of 1-8 mass parts. It is more preferable. When the content is in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the resin content, a resin composition having better printability can be obtained. When the content is less than 1 part by mass, the effect as a foaming aid of the functional group-containing fatty acid metal salt is not sufficiently obtained, and the decomposition efficiency of the foaming agent tends to decrease, and when the content is more than 10 parts by mass. The printability tends to decrease due to the influence of the functional group-containing fatty acid metal salt present on the surface of the resin sheet formed into a film.
本実施形態の発泡助剤は、本願発明による効果が損なわれない範囲であれば、上述した官能基含有脂肪酸金属塩以外の発泡助剤を含んでいてもよい。そのような発泡助剤としては、例えば、ステアリン酸、ラウリン酸等の脂肪族系、ステアリン酸アミド、オレイン酸アミド等の脂肪酸アミド系、ステアリン酸亜鉛、ラウリン酸カルシウム、オクチル酸マグネシウム等の脂肪酸金属塩系のほか、ビウレア等の尿素系、塩化亜鉛等の金属塩化物、酸化亜鉛等の金属酸化物などが挙げられる。 The foaming aid of the present embodiment may contain a foaming aid other than the above-described functional group-containing fatty acid metal salt as long as the effects of the present invention are not impaired. Examples of such foaming aids include aliphatic systems such as stearic acid and lauric acid, fatty acid amide systems such as stearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate, calcium laurate, and magnesium octylate. In addition to the system, urea systems such as biurea, metal chlorides such as zinc chloride, metal oxides such as zinc oxide, and the like can be given.
また、本実施形態に係る官能基含有脂肪酸金属塩の含有量としては、発泡助剤の総量１００質量部に対して、３０〜１００質量部の範囲内であることが好ましく、５０〜１００質量部の範囲であることがより好ましい。当該含有量が発泡助剤の総量１００質量部に対して３０〜１００質量部の範囲内であれば、印刷適性を十分維持しつつ、より良好な施工性及び発泡倍率を有する樹脂組成物を得ることができる。 Moreover, as content of the functional group containing fatty acid metal salt which concerns on this embodiment, it is preferable to exist in the range of 30-100 mass parts with respect to 100 mass parts of total amounts of foaming adjuvant, and 50-100 mass parts. More preferably, it is the range. If the content is in the range of 30 to 100 parts by mass with respect to 100 parts by mass of the total amount of foaming aid, a resin composition having better workability and expansion ratio is obtained while sufficiently maintaining printability. be able to.
本実施形態に係る発泡助剤の総量としては、発泡剤１００質量部に対して、２０〜１５０質量部の範囲内であることが好ましく、２０〜１００質量部の範囲内であることがより好ましい。当該含有量が発泡剤１００質量部に対して２０〜１００質量部の範囲内であれば、発泡壁紙製造時における発泡温度を下げすぎることなく発泡後の呈色をより効率的に抑えることができ、印刷適性も良好に保つことができる。発泡助剤の含有量が発泡剤１００質量部に対して１５０質量部以下であれば、発泡剤の分解温度が低下しすぎることによる発泡壁紙製造時の機械的及び材料的制約を小さくすることができ、２０質量部以上であれば、発泡工程における加熱を過度に長期化、高温化することなく十分な発泡性を得ることができ、基材の熱劣化や樹脂の酸化劣化による変色を抑制することができる。 The total amount of the foaming aid according to the present embodiment is preferably in the range of 20 to 150 parts by mass, more preferably in the range of 20 to 100 parts by mass with respect to 100 parts by mass of the foaming agent. . If the content is in the range of 20 to 100 parts by mass with respect to 100 parts by mass of the foaming agent, coloration after foaming can be more efficiently suppressed without excessively reducing the foaming temperature during the production of the foam wallpaper. Also, the printability can be kept good. If the content of the foaming aid is 150 parts by mass or less with respect to 100 parts by mass of the foaming agent, the mechanical and material restrictions during the production of the foamed wallpaper due to the excessive decrease in the decomposition temperature of the foaming agent can be reduced. If it is 20 parts by mass or more, sufficient foamability can be obtained without excessively long heating and high temperature in the foaming step, and discoloration due to thermal degradation of the base material and oxidation degradation of the resin is suppressed. be able to.
本実施形態に係る樹脂分としては、燃焼時にダイオキシン等の有毒ガスの発生を防ぐ観点から、非塩素系熱可塑性樹脂を含むことが好ましい。非塩素系熱可塑性樹脂としては、例えば、エチレン単独重合体、エチレンと他のオレフィンとの共重合体、ポリオレフィン樹脂（ポリプロピレン、ポリブテン、ポリメチルペンテン等の単一オレフィン重合体、２種以上のオレフィンのランダム又はブロック共重合体など）、スチレン系樹脂（ポリスチレン、アクリロニトリル・スチレン共重合体（ＡＳ）、アクリロニトリル・ブタジエン・スチレン共重合体（ＡＢＳ）等）、エチレンコポリマー（エチレン−酢酸ビニル共重合体、エチレン−メチルメタクリレート共重合体、エチレン−アクリル酸共重合体、エチレン−エチルアクリレート共重合体、エチレン−メチルアクリレート共重合体、エチレン−メタクリル酸共重合体等）などが挙げられる。これらは１種を単独で、又は２種以上を併用して用いることができる。 The resin component according to the present embodiment preferably contains a non-chlorine thermoplastic resin from the viewpoint of preventing generation of toxic gas such as dioxin during combustion. Non-chlorinated thermoplastic resins include, for example, ethylene homopolymers, copolymers of ethylene and other olefins, polyolefin resins (single olefin polymers such as polypropylene, polybutene, polymethylpentene, etc., two or more olefins Random or block copolymer), styrene resin (polystyrene, acrylonitrile / styrene copolymer (AS), acrylonitrile / butadiene / styrene copolymer (ABS), etc.), ethylene copolymer (ethylene-vinyl acetate copolymer) , Ethylene-methyl methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, etc.). These can be used alone or in combination of two or more.
中でも、本実施形態に係る樹脂分は、エチレン単独重合体又はエチレンと他のオレフィンとの共重合体を含むことが好ましい。エチレン単独重合体又はエチレンと他のオレフィンとの共重合体を用いることにより、ベース樹脂の表面エネルギーが大きいためにブリードアウトの低減による親インク性の向上効果がより大きく発揮される。 Especially, it is preferable that the resin part which concerns on this embodiment contains the ethylene homopolymer or the copolymer of ethylene and another olefin. By using an ethylene homopolymer or a copolymer of ethylene and another olefin, since the surface energy of the base resin is large, the effect of improving the ink affinity due to the reduction of bleed out is exhibited more greatly.
エチレン単独重合体及びエチレンと他のオレフィンとの共重合体は、無極性の非ハロゲン系熱可塑性樹脂であり、これらを用いることで、充填剤を増量した場合の粘度上昇が抑えられるため、高品質の壁紙を安定して生産することができる。 Ethylene homopolymers and copolymers of ethylene and other olefins are non-polar non-halogen thermoplastic resins, and by using these, it is possible to suppress an increase in viscosity when the amount of filler is increased. Quality wallpaper can be produced stably.
エチレン単独重合体としては、例えば、高圧法で合成された低密度ポリエチレン、中低圧法で合成されたコモノマーを含まない高密度ポリエチレン等が挙げられる。中でも、低密度ポリエチレンが好ましい。 Examples of the ethylene homopolymer include low density polyethylene synthesized by a high pressure method, high density polyethylene not containing a comonomer synthesized by a medium pressure method, and the like. Among these, low density polyethylene is preferable.
低密度ポリエチレンは、例えば、密度０．９１ｇ／ｃｍ３以上０．９４ｇ／ｃｍ３以下の範囲にあるものが挙げられる。低密度ポリエチレンの密度は、好ましくは密度０．９１ｇ／ｃｍ３以上０．９３ｇ／ｃｍ３以下であり、より好ましくは密度０．９２ｇ／ｃｍ３以上０．９３ｇ／ｃｍ３以下である。低密度ポリエチレンの分子量、融点、メルトフローレート（ＭＦＲ）等については特に制限されないが、融点については、５０℃〜１４０℃が好ましく、６０℃から１１０℃がより好ましい。融点が１４０℃以下であれば樹脂を溶融して成型する際により高温で溶融する必要がなく、発泡剤が成型中に分解してしまうという可能性が少ない。一方、融点が５０℃以上であれば、実使用上の熱耐久性が十分に得られる。ＭＦＲについては３〜１５０のものが好ましく、４〜１００のものがより好ましい。ＭＦＲが３以上であれば、成型時に生じるせん断発熱を抑えることができ、加工温度の制御が容易になり、成型中に発泡剤が分解してしまうという可能性が少ない。一方、ＭＦＲが１５０以下であれば、製造された発泡壁紙の機械強度が保たれ、施工性及び耐久性に優れる。 Low density polyethylene, for example, those in the density of 0.91 g / cm 3 or more 0.94 g / cm 3 or less. The density of low-density polyethylene is preferably not less density 0.91 g / cm 3 or more 0.93 g / cm 3, more preferably less density 0.92 g / cm 3 or more 0.93 g / cm 3. The molecular weight, melting point, melt flow rate (MFR) and the like of the low density polyethylene are not particularly limited, but the melting point is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 110 ° C. If the melting point is 140 ° C. or lower, it is not necessary to melt the resin and mold it at a higher temperature, and the foaming agent is less likely to decompose during molding. On the other hand, if the melting point is 50 ° C. or higher, sufficient heat durability in actual use can be obtained. The MFR is preferably from 3 to 150, more preferably from 4 to 100. If the MFR is 3 or more, shear heat generated during molding can be suppressed, the processing temperature can be easily controlled, and there is little possibility that the foaming agent will be decomposed during molding. On the other hand, if the MFR is 150 or less, the mechanical strength of the produced foamed wallpaper is maintained, and the workability and durability are excellent.
低密度ポリエチレンとしては、例えば、ノバテックＬＤ ＬＣ８０２Ａ、ノバテックＬＤ ＬＣ６０４（以上、日本ポリエチレン製）、宇部ポリエチレン Ｊ２５１６（宇部丸善ポリエチレン製）等の市販品を用いることができる。 As low-density polyethylene, for example, commercially available products such as Novatec LD LC802A, Novatec LD LC604 (above, made by Nippon Polyethylene), Ube Polyethylene J2516 (made by Ube Maruzen Polyethylene) can be used.
エチレンと他のオレフィンとの共重合体は、例えば直鎖状低密度ポリエチレン、超低密度ポリエチレン、コモノマーとの共重合で得られた高密度ポリエチレン等が挙げられ、これらは１種を単独で、又は２種以上を併用して用いることができる。中でも、超低密度ポリエチレンが好ましい。 Examples of the copolymer of ethylene and other olefins include linear low density polyethylene, ultra-low density polyethylene, high density polyethylene obtained by copolymerization with a comonomer, and the like. Alternatively, two or more kinds can be used in combination. Among these, ultra-low density polyethylene is preferable.
超低密度ポリエチレンとしては、例えば、密度０．８８ｇ／ｃｍ３以上０．９１ｇ／ｃｍ３未満の範囲にあるものが挙げられる。超低密度ポリエチレンの密度は、好ましくは密度０．８８ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下であり、より好ましくは密度０．８９ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下である。超低密度ポリエチレンの分子量、融点、ＭＦＲ等については特に制限されないが、融点については５０〜１４０℃が好ましく、６０〜１１０℃がより好ましい。融点が１４０℃以下であれば樹脂を溶融して成型する際により高温で溶融する必要がなく、発泡剤が成型中に分解してしまうという可能性が少ない。一方、融点が５０℃以上であれば、実使用上の熱耐久性が十分に得られる。ＭＦＲについては３〜１５０のものが好ましく、４〜１００のものがより好ましい。ＭＦＲが３以上であれば、成型時に生じるせん断発熱を抑えることができ、加工温度の制御が容易になり、成型中に発泡剤が分解してしまうという可能性が少ない。一方、ＭＦＲが１５０以下であれば、製造された発泡壁紙の機械強度が保たれ、施工性及び耐久性に優れる。 The ultra low density polyethylene, for example, those in the range of less than the density 0.88 g / cm 3 or more 0.91 g / cm 3. Density ultra low density polyethylene is preferably not less density 0.88 g / cm 3 or more 0.90 g / cm 3, more preferably less density 0.89 g / cm 3 or more 0.90 g / cm 3. The molecular weight, melting point, MFR and the like of the ultra-low density polyethylene are not particularly limited, but the melting point is preferably 50 to 140 ° C, more preferably 60 to 110 ° C. If the melting point is 140 ° C. or lower, it is not necessary to melt the resin and mold it at a higher temperature, and the foaming agent is less likely to decompose during molding. On the other hand, if the melting point is 50 ° C. or higher, sufficient heat durability in actual use can be obtained. The MFR is preferably from 3 to 150, more preferably from 4 to 100. If the MFR is 3 or more, shear heat generated during molding can be suppressed, the processing temperature can be easily controlled, and there is little possibility that the foaming agent will be decomposed during molding. On the other hand, if the MFR is 150 or less, the mechanical strength of the produced foamed wallpaper is maintained, and the workability and durability are excellent.
超低密度ポリエチレンとしては、例えば、タフマー ＤＦ１４０、ＤＦ９４０、ＤＦ７３５０（いずれも三井化学株式会社製）、カーネル ＫＪ−６４０Ｔ（日本ポリエチレン株式会社製）、エクセレンＦＸ ＣＸ５５０８（住友化学株式会社製）、エンゲージ ８４００／８４０７（ダウ・ケミカル社製）、エボリューＰ ＳＰ９０１００（株式会社プライムポリマー製）、ルミタック０９Ｌ５４Ａ（東ソー株式会社製）等の市販品を用いることができる。 Examples of the ultra-low density polyethylene include TAFMER DF140, DF940, DF7350 (all manufactured by Mitsui Chemicals), Kernel KJ-640T (manufactured by Nippon Polyethylene Co., Ltd.), Excellen FX CX5508 (manufactured by Sumitomo Chemical Co., Ltd.), Engage 8400. / 8407 (manufactured by Dow Chemical Co., Ltd.), Evolue P SP90100 (manufactured by Prime Polymer Co., Ltd.), LumiTac 09L54A (manufactured by Tosoh Corporation) and the like can be used.
樹脂分の含有量は、樹脂の合計量が、樹脂組成物全量を基準として、２０〜８０質量％であることが好ましく、４０〜７５質量％であることがより好ましく、５０〜７０質量％であることが更に好ましい。なお、この場合、樹脂分は架橋されていてもよい。 The total resin content is preferably 20 to 80% by mass, more preferably 40 to 75% by mass, and 50 to 70% by mass based on the total amount of the resin composition. More preferably it is. In this case, the resin component may be cross-linked.
本実施形態に係る多価アルコールとは、分子内に２つ以上の水酸基を有する化合物を指す。分子内の水酸基の数については特に制限はないが、水酸基の数が少なすぎると変色を抑えるための相互作用を形成するためにより多量の多価アルコールが必要になり、一方、水酸基の数が多すぎると多価アルコール自身の極性や融点、粘度等が増大してベース樹脂との相溶性が低下する。以上の観点から、多価アルコールは、分子内に３〜５個の水酸基を有する化合物であることが好ましい。 The polyhydric alcohol according to this embodiment refers to a compound having two or more hydroxyl groups in the molecule. The number of hydroxyl groups in the molecule is not particularly limited, but if the number of hydroxyl groups is too small, a larger amount of polyhydric alcohol is required to form an interaction for suppressing discoloration, while the number of hydroxyl groups is large. If it is too high, the polarity, melting point, viscosity, etc. of the polyhydric alcohol itself will increase and the compatibility with the base resin will decrease. From the above viewpoint, the polyhydric alcohol is preferably a compound having 3 to 5 hydroxyl groups in the molecule.
本実施形態に係る多価アルコールとしては、例えば、エチレングリコール、ビスフェノールＡ、ペンタエリスリトール、ソルビトール、ソルビタン等の単分子多価アルコール、ポリエチレングリコール、ポリオキシエチレンソルビタン等の高分子多価アルコール、これらの多価アルコールのモノエステルやジエステル等が挙げられる。これらはベース樹脂の粘度や融点、極性等に応じて適宜選択できるが、上述した好ましい水酸基の数等に鑑みると、ペンタエリスリトール、ソルビタン及びこれらのエステルからなる群より選択される少なくとも１種を用いることが好ましい。エステルの場合、炭素数８〜３０の脂肪酸とのエステルが好ましい。 Examples of the polyhydric alcohol according to the present embodiment include monomolecular polyhydric alcohols such as ethylene glycol, bisphenol A, pentaerythritol, sorbitol, and sorbitan, polymeric polyhydric alcohols such as polyethylene glycol and polyoxyethylene sorbitan, and the like. Examples thereof include monoesters and diesters of polyhydric alcohols. These can be appropriately selected according to the viscosity, melting point, polarity and the like of the base resin, but in view of the number of preferable hydroxyl groups described above, at least one selected from the group consisting of pentaerythritol, sorbitan and esters thereof is used. It is preferable. In the case of an ester, an ester with a fatty acid having 8 to 30 carbon atoms is preferred.
本実施形態に係る多価アルコールの含有量としては、上記樹脂分１００質量部に対して０．１〜１５質量部の範囲内であることが好ましく、１〜８質量部の範囲内であることがより好ましい。多価アルコールの含有量が、樹脂分１００質量部に対して０．１〜１５質量部の範囲内であれば、多価アルコールによるブリードアウトを制限しながら発泡工程での呈色物質の発生をより効率的に抑えることができる。 As content of the polyhydric alcohol which concerns on this embodiment, it is preferable to exist in the range of 0.1-15 mass parts with respect to 100 mass parts of said resin parts, and it exists in the range of 1-8 mass parts. Is more preferable. If the content of the polyhydric alcohol is within the range of 0.1 to 15 parts by mass with respect to 100 parts by mass of the resin component, the generation of the colored substance in the foaming process is limited while restricting the bleed out by the polyhydric alcohol. It can be suppressed more efficiently.
また、本実施形態に係る多価アルコールの含有量としては、官能基含有脂肪酸金属塩１００質量部に対して３０〜２００質量部の範囲内であることが好ましく、５０〜１２０質量部の範囲内であることがより好ましい。多価アルコールの含有量が、官能基含有脂肪酸金属塩１００質量部に対して３０〜２００質量部の範囲内であれば、多価アルコールによるブリードアウトを制限しながら発泡工程での呈色物質の発生をより効率的に抑えることができ、印刷適性も良好に保つことができる。多価アルコールの含有量が官能基含有脂肪酸金属塩１００質量部に対して３０質量部以上であれば、呈色抑制効果が得られやすくなり、２００質量部以下であれば、多価アルコールによるブリードアウトを制限することができる。 Moreover, as content of the polyhydric alcohol which concerns on this embodiment, it is preferable to exist in the range of 30-200 mass parts with respect to 100 mass parts of functional group containing fatty acid metal salts, and within the range of 50-120 mass parts. It is more preferable that If the content of the polyhydric alcohol is within the range of 30 to 200 parts by mass with respect to 100 parts by mass of the functional group-containing fatty acid metal salt, the coloration substance in the foaming step is limited while restricting the bleed out by the polyhydric alcohol. Generation | occurrence | production can be suppressed more efficiently and printability can also be maintained favorable. If the content of the polyhydric alcohol is 30 parts by mass or more with respect to 100 parts by mass of the functional group-containing fatty acid metal salt, a coloration suppressing effect is easily obtained. You can limit out.
また、本実施形態に係る樹脂組成物には、必要に応じて顔料等を添加して着色してもよい。顔料の添加による着色は、透明であってもよいし、半透明であってもよいし、不透明であってもよい。顔料としては、例えば、酸化鉄、カーボンブラック等の無機顔料、又はアニリンブラック、フタロシアニンブルー等の有機顔料などを挙げることができる。 In addition, the resin composition according to the present embodiment may be colored by adding a pigment or the like as necessary. Coloring by adding a pigment may be transparent, translucent, or opaque. Examples of the pigment include inorganic pigments such as iron oxide and carbon black, and organic pigments such as aniline black and phthalocyanine blue.
顔料の添加量としては、樹脂組成物全量を基準として、好ましくは５〜５０質量％、より好ましくは１０〜３０質量％である。 The addition amount of the pigment is preferably 5 to 50% by mass, more preferably 10 to 30% by mass based on the total amount of the resin composition.
また、樹脂組成物には、必要に応じて、難燃剤、セル調整剤、安定剤、滑剤等の周知の添加剤を用いることができる。 Moreover, well-known additives, such as a flame retardant, a cell regulator, a stabilizer, and a lubricant, can be used for a resin composition as needed.
難燃剤としては、例えば、水酸化マグネシウム、水酸化アルミニウム等の金属酸化物系難燃剤、リン酸エステル系等のリン系難燃剤、テトラブロモビスフェノールＡ等の臭素系難燃剤などが挙げられる。 Examples of the flame retardant include metal oxide flame retardants such as magnesium hydroxide and aluminum hydroxide, phosphorus flame retardants such as phosphate ester, and bromine flame retardants such as tetrabromobisphenol A.
セル調整剤としては、例えば、リン酸エステル系化合物、アクリル酸エステル系樹脂、メタクリル酸エステル系樹脂等が挙げられる。セル調整剤は、アデカスタブＨＰ−１０（株式会社ＡＤＥＫＡ製）、Ｉｒｇａｆｏｓ ３８（Ｂ．Ａ．Ｓ．Ｆ． Ｊａｐａｎ製）、ＪＰＰ−２０００（城北化学工業株式会社製）等の市販品を用いることができる。 Examples of the cell regulator include phosphate ester compounds, acrylic ester resins, and methacrylic ester resins. Commercially available products such as ADK STAB HP-10 (manufactured by ADEKA), Irgafos 38 (manufactured by BASF Japan), and JPP-2000 (manufactured by Johoku Chemical Industry Co., Ltd.) can be used as the cell regulator. it can.
安定剤としては、例えば、フェノール／アミン系酸化防止剤、ヒンダードアミン系光安定剤等のラジカル捕捉剤、リン系、イオウ系等の過酸化物分解剤、ベンゾトリアゾール系、ヒドロキシフェニルトリアジン系、ベンゾフェノン系紫外線吸収剤などが挙げられる。 Stabilizers include, for example, radical scavengers such as phenol / amine antioxidants, hindered amine light stabilizers, peroxide decomposers such as phosphorus and sulfur, benzotriazoles, hydroxyphenyltriazines, and benzophenones. Examples include ultraviolet absorbers.
滑剤としては、例えば、ステアリン酸、ラウリン酸等の脂肪酸系、ステアリン酸アミド、オレイン酸アミド等の脂肪酸アミド系、ステアリン酸亜鉛、ラウリン酸カルシウム、オクチル酸亜鉛等の脂肪酸金属塩系の滑剤などが挙げられる。 Examples of the lubricant include fatty acid-based lubricants such as stearic acid and lauric acid, fatty acid amide-based compounds such as stearic acid amide and oleic acid amide, and fatty acid metal salt-based lubricants such as zinc stearate, calcium laurate and zinc octylate. It is done.
［樹脂シート］
本実施形態に係る樹脂シートは、上記本実施形態に係る樹脂組成物から形成されるものである。本実施形態に係る樹脂シートは、例えば、上記本実施形態に係る樹脂組成物を押出製膜して得ることができる。
[Resin sheet]
The resin sheet according to the present embodiment is formed from the resin composition according to the present embodiment. The resin sheet according to the present embodiment can be obtained, for example, by extrusion film-forming the resin composition according to the present embodiment.
押出製膜の方法としては、例えば、Ｔダイ押出法、Ｔダイ押出同時ラミネーション法、Ｔダイ押出タンデムラミネーション法、円形ダイ押出法、円形ダイインフレーション押出法等の押出成形が挙げられる。 Examples of the extrusion film forming method include extrusion molding such as T-die extrusion method, T-die extrusion simultaneous lamination method, T-die extrusion tandem lamination method, circular die extrusion method, and circular die inflation extrusion method.
本実施形態に係る樹脂シートは、押出成形以外に、射出成形、プレス成形、ブロー成形、カレンダ成形、コーティング成形、キャスト成形、ディッピング成形、真空成形、トランスファ成形などの公知の成形方法によっても製造することができる。 The resin sheet according to the present embodiment is produced not only by extrusion molding but also by known molding methods such as injection molding, press molding, blow molding, calendar molding, coating molding, cast molding, dipping molding, vacuum molding, transfer molding, and the like. be able to.
樹脂組成物は、各成分を押出機で溶融・混練・分散させた後に、適宜ペレット化したものを用いることができる。押出機は単軸押出機でも２軸押出機でもよいが、生産性や品質への影響を考慮した場合、２軸押出機が望ましい。 The resin composition can be used by appropriately pelletizing each component after melting, kneading and dispersing with an extruder. The extruder may be a single-screw extruder or a twin-screw extruder, but a twin-screw extruder is preferable in view of the influence on productivity and quality.
押出製膜の条件としては、押出温度１００〜１６０℃、押出圧力２〜５０ＭＰａが挙げられる。発泡剤成分の分解を抑制しつつポリエチレン成分の融点以上とする観点から、押出温度は１１０〜１５０℃が好ましく、１２０〜１４０℃がより好ましい。また、押出安定性の観点から、押出圧力は、３〜４０ＭＰａが好ましく、３〜３０ＭＰａがより好ましい。 Extrusion film forming conditions include an extrusion temperature of 100 to 160 ° C. and an extrusion pressure of 2 to 50 MPa. From the viewpoint of setting the melting point of the polyethylene component to be equal to or higher than the melting point of the polyethylene component while suppressing the decomposition of the foaming agent component, the extrusion temperature is preferably 110 to 150 ° C, more preferably 120 to 140 ° C. From the viewpoint of extrusion stability, the extrusion pressure is preferably 3 to 40 MPa, more preferably 3 to 30 MPa.
樹脂シートの厚みは、用途に応じて適宜設定することができるが、例えば、発泡壁紙用途であれば５０〜２００μｍとすることができる。 Although the thickness of a resin sheet can be suitably set according to a use, if it is a foam wallpaper use, it can be 50-200 micrometers, for example.
樹脂シートは、架橋処理が施されていてもよい。架橋処理としては、電子線照射処理、過熱蒸気処理等の加熱処理が挙げられる。樹脂組成物がシラン架橋性樹脂を含む場合には、過熱蒸気処理、水架橋処理を行うことができる。 The resin sheet may be subjected to a crosslinking treatment. Examples of the crosslinking treatment include heat treatment such as electron beam irradiation treatment and superheated steam treatment. When the resin composition contains a silane crosslinkable resin, superheated steam treatment and water crosslinking treatment can be performed.
電子線照射処理は、例えば、製膜した樹脂シートの片面側から、又は両面から電子線を照射することにより、樹脂シートに架橋処理を施すことができる。電子線照射の条件としては、発泡樹脂層の厚みにもよるが、加速電圧１５０〜３００ｋＶ、照射線量１０〜１００ｋＧｙが好ましい。加速電圧が上記範囲内であれば、電子線を樹脂シートの厚み方向深くまで十分に到達させることができ、なおかつ裏打紙への電子線による劣化を抑制することができる。また、照射線量が上記範囲内であれば、樹脂シートの黄変や機械物性の変化を抑制しつつ、樹脂シートに所望の架橋を施すことが容易となる。 In the electron beam irradiation treatment, for example, the resin sheet can be crosslinked by irradiating an electron beam from one side or both sides of the formed resin sheet. Although the electron beam irradiation conditions depend on the thickness of the foamed resin layer, an acceleration voltage of 150 to 300 kV and an irradiation dose of 10 to 100 kGy are preferable. If the acceleration voltage is within the above range, the electron beam can be sufficiently reached deep in the thickness direction of the resin sheet, and deterioration due to the electron beam on the backing paper can be suppressed. Moreover, if irradiation dose is in the said range, it will become easy to give desired bridge | crosslinking to a resin sheet, suppressing the yellowing of a resin sheet and the change of a mechanical physical property.
過熱蒸気処理は、例えば、１３０℃〜２８０℃の環境下で２０秒から１５分間、過熱蒸気（過熱水蒸気ともいう）処理する方法等が挙げられる。過熱蒸気処理は、例えば、過熱蒸気雰囲気下にシート状物を配し、シート状物に過熱蒸気を接触させる方法が挙げられる。また、水架橋させる方法としては、湿度６０％以上の環境下、４０℃〜７０℃の温度域で１日〜１か月養生させて水架橋させる方法が挙げられ、具体的には、４０℃９０％の恒温恒湿槽の環境下において養生させて水架橋させる方法が挙げられる。 Examples of the superheated steam treatment include a method in which superheated steam (also referred to as superheated steam) is treated for 20 seconds to 15 minutes in an environment of 130 ° C. to 280 ° C. The superheated steam treatment includes, for example, a method in which a sheet-like material is arranged in a superheated steam atmosphere and the superheated steam is brought into contact with the sheet-like material. Moreover, as a method of water-crosslinking, there is a method of water-crosslinking by curing for 1 day to 1 month in a temperature range of 40 ° C. to 70 ° C. in an environment with a humidity of 60% or more. There is a method of curing and hydrocrosslinking in an environment of a 90% constant temperature and humidity chamber.
樹脂シートの架橋処理は、樹脂組成物を製膜したものに施してもよく、後述する積層シートにした後に施してもよい。 The crosslinking treatment of the resin sheet may be performed on the resin composition formed into a film, or may be performed after forming a laminated sheet to be described later.
［積層シート］
本実施形態に係る積層シートは、基材と、基材上に設けられた上記樹脂シートと、を備える。当該積層シートは、樹脂シートを、基材上にラミネートして得ることができる。ラミネートの方法としては、特に限定されるものではないが、樹脂シートと基材とを、熱プレス機等を用いて熱圧着を行う方法、過熱蒸気を用いて圧着を行う方法等が挙げられる。過熱蒸気を用いて圧着を行う方法によれば、過熱蒸気によってシート状物の表面の溶融状態を保ったまま基材上へラミネートすることが可能となり、そのレベリング効果によって、密着させる基材の表面の凹凸が樹脂シートに転写されることを抑制することができる。また、樹脂シートがシラン架橋性樹脂を含む場合は、過熱蒸気によってシラン架橋性樹脂を効率よく架橋させることができる。
[Laminated sheet]
The laminated sheet according to the present embodiment includes a base material and the resin sheet provided on the base material. The laminated sheet can be obtained by laminating a resin sheet on a substrate. The laminating method is not particularly limited, and examples thereof include a method in which a resin sheet and a base material are subjected to thermocompression bonding using a hot press machine, a method in which pressure bonding is performed using superheated steam, and the like. According to the method of pressure bonding using superheated steam, it becomes possible to laminate onto the base material while maintaining the molten state of the surface of the sheet-like material with superheated steam, and the surface of the base material to be adhered by the leveling effect It can suppress that the unevenness | corrugation of is transferred to a resin sheet. Moreover, when a resin sheet contains a silane crosslinkable resin, a silane crosslinkable resin can be bridge | crosslinked efficiently by superheated steam.
上記基材としては、従来ある壁紙用裏打紙等の紙基材として通常使用されているものであれば特に限定されずに使用可能である。このような基材としては、例えば、スルファミン酸グアニジン、リン酸グアニジン等の水溶性難燃剤を含浸させたパルプ主体の難燃紙、又は炭酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム等の無機質剤を混抄した無機質紙などが挙げられる。これらの秤量は、５０〜３００ｇ／ｍ２であってもよく、６０〜１６０ｇ／ｍ２であってもよい。 The base material is not particularly limited as long as it is usually used as a paper base material such as a conventional backing paper for wallpaper. As such a substrate, for example, a pulp-based flame retardant paper impregnated with a water-soluble flame retardant such as guanidine sulfamate or guanidine phosphate, or an inorganic agent such as magnesium carbonate, aluminum hydroxide, magnesium hydroxide or the like. Examples include mixed paper. These weighings may be 50 to 300 g / m 2 or 60 to 160 g / m 2 .
また、基材と上記樹脂シートとの接着性を向上させる観点から、基材の表面で樹脂シートを設ける側の面には、例えば、コロナ放電処理、プラズマ処理、オゾン処理等の易接着処理を施してもよく、アクリル−ブチル共重合体、イソシアネートとポリオールとからなるポリウレタン等から形成される易接着処理層を設けてもよい。 Further, from the viewpoint of improving the adhesion between the base material and the resin sheet, the surface on the side of the base material where the resin sheet is provided is subjected to easy adhesion processing such as corona discharge treatment, plasma treatment, ozone treatment, etc. Alternatively, an easy adhesion treatment layer formed from an acrylic-butyl copolymer, polyurethane composed of isocyanate and polyol, or the like may be provided.
［発泡壁紙］
本実施形態に係る発泡壁紙は、基材と、基材上に設けられた発泡樹脂層と、を備える。このような発泡壁紙は、例えば、上述した樹脂シートを、基材上にラミネートして積層シートを得る工程と、上記樹脂シートに含まれる発泡剤を発泡させることにより、発泡樹脂層を形成する工程と、を備える、製造方法によって得ることができる。
[Foam wallpaper]
The foam wallpaper according to the present embodiment includes a base material and a foamed resin layer provided on the base material. Such foam wallpaper includes, for example, a step of laminating the above-described resin sheet on a substrate to obtain a laminated sheet, and a step of forming a foamed resin layer by foaming a foaming agent contained in the resin sheet. And can be obtained by a manufacturing method.
発泡剤の発泡は、樹脂シートを加熱することにより行うことができる。加熱条件としては、当該樹脂シートを構成する成分によって適宜設定することができ、特に制限はないが、１６０℃〜２８０℃で１０秒〜１２０秒間加熱することが好ましく、２２０℃〜２４０℃で２０秒〜４０秒間加熱することがより好ましく、２２０℃で４０秒間加熱することが更に好ましい。 Foaming of the foaming agent can be performed by heating the resin sheet. The heating conditions can be appropriately set depending on the components constituting the resin sheet, and are not particularly limited. However, heating is preferably performed at 160 ° C. to 280 ° C. for 10 seconds to 120 seconds, and 220 ° C. to 240 ° C. at 20 ° C. It is more preferable to heat for 2 seconds to 40 seconds, and further more preferable to heat at 220 ° C. for 40 seconds.
他の実施形態として、発泡壁紙は、上記積層シートにおける樹脂シートに含まれる発泡剤を発泡させることにより、発泡樹脂層を形成する工程を備える方法によっても得ることができる。 As another embodiment, the foam wallpaper can be obtained by a method including a step of forming a foamed resin layer by foaming a foaming agent contained in the resin sheet in the laminated sheet.
さらに、本実施形態に係る発泡壁紙において、発泡樹脂層の基材とは反対側の面は凹凸形状を有していてもよい。凹凸形状を設ける方法としては、特に制限されるものではないが、例えば、加熱発泡の際の熱を利用して、表面側を冷却エンボスロールとし、基材側をゴムロールとしておき、２つのトールでニップし（エンボス加工し）冷却することにより、表面に凹凸形状を形成する方法等が挙げられる。凹凸形状としては、特に制限されるものではないが、例えば、木目板導管溝、石板表面凹凸、布表面テクスチャア、梨地、砂目、ヘアライン、万線条溝等が挙げられ、目的とする意匠により適宜選択可能である。 Furthermore, in the foamed wallpaper according to the present embodiment, the surface of the foamed resin layer opposite to the base material may have an uneven shape. The method for providing the uneven shape is not particularly limited. For example, by using heat at the time of heating and foaming, the surface side is a cooling embossing roll, the base material side is a rubber roll, Examples of the method include forming a concavo-convex shape on the surface by niping (embossing) and cooling. The uneven shape is not particularly limited, and examples thereof include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grained grain, a hairline, and a straight line groove. Can be selected as appropriate.
本実施形態に係る発泡壁紙は、模様層及び表面保護層を設けてもよい。模様層及び表面保護層は、公知の材料を使用して適宜設けることができる。本発明の目的が達成できるのであれば、模様層及び表面保護層を設けなくともよい。模様層及び表面保護層は、グラビアコーティング等の公知の印刷技術を用いて設けることが可能である。なお、模様層及び表面保護層は、発泡剤を発泡させる前に設けることができる。 The foamed wallpaper according to the present embodiment may be provided with a pattern layer and a surface protective layer. The pattern layer and the surface protective layer can be appropriately provided using known materials. If the object of the present invention can be achieved, the pattern layer and the surface protective layer may not be provided. The pattern layer and the surface protective layer can be provided using a known printing technique such as gravure coating. In addition, a pattern layer and a surface protective layer can be provided before foaming a foaming agent.
以下、実施例及び比較例を示して本発明を具体的に説明する。ただし、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.
［発泡壁紙の作製］
（実施例１〜５、比較例１〜３）
コートハンガータイプのマニュホールドを有するＴダイを用いて、スクリュー径（Ｄ）６５ｍｍ、Ｌ／Ｄ＝３２のバリアタイプスクリューを用い、表１に示される組成（表中の数値は質量部を示す）を有する樹脂組成物を、押出温度１２５℃、厚み１００μｍで製膜し、樹脂シートをそれぞれ得た。
[Production of foam wallpaper]
(Examples 1-5, Comparative Examples 1-3)
Using a T-die having a coat hanger type manifold, using a barrier type screw with a screw diameter (D) of 65 mm and L / D = 32, the composition shown in Table 1 (the numerical values in the table indicate parts by mass) A resin composition having a thickness of 100 μm was formed at an extrusion temperature of 125 ° C. to obtain resin sheets, respectively.
なお、上記樹脂シートはそれぞれ、加速電圧２００ｋＶ、照射線量５０ｋＧｙで電子線の照射をし、樹脂分を架橋させた。 Each of the resin sheets was irradiated with an electron beam at an acceleration voltage of 200 kV and an irradiation dose of 50 kGy to crosslink the resin component.
次に裏打紙（ＫＪ特種紙製、ＷＫ−６６５１ＨＴ、重量６５ｇ／ｃｍ２）上に、実施例及び比較例で製膜した樹脂シートを置き、１１０℃で加熱した熱プレス機でプレス圧力５ＭＰａの条件で２分間プレスして熱融着させ、積層シートを得た。 Next, on the backing paper (KJ Special Paper, WK-6651HT, weight 65 g / cm 2 ), the resin sheets formed in Examples and Comparative Examples were placed and heated at 110 ° C. with a press pressure of 5 MPa. The laminate sheet was obtained by pressing for 2 minutes under the conditions and heat-sealing.
得られた積層シートの樹脂シート側表面にコロナ放電処理を施した後、グラビア印刷機により水性インキ（大日精化工業株式会社製、ハイドリックＷＰ）を用いて絵柄模様を印刷した。次に、それぞれの積層シートを２４０℃のオーブンで２５秒間加熱し、発泡剤を発泡させて、発泡壁紙を作製した。 After the corona discharge treatment was performed on the resin sheet side surface of the obtained laminated sheet, a pattern was printed using a water-based ink (Daiichi Seika Kogyo Co., Ltd., Hydrick WP) with a gravure printing machine. Next, each laminated sheet was heated in an oven at 240 ° C. for 25 seconds to foam the foaming agent, thereby producing a foamed wallpaper.
表１に示される各成分は以下の材料を用いた。 The following materials were used for each component shown in Table 1.
［低密度ポリエチレン］
樹脂Ａ：ノバテックＬＤ ＬＣ６０４（日本ポリエチレン株式会社製、商品名、密度＝０．９１８ｇ／ｃｍ３）
[Low density polyethylene]
Resin A: Novatec LD LC604 (manufactured by Nippon Polyethylene Co., Ltd., trade name, density = 0.918 g / cm 3 )
［超低密度ポリエチレン］
樹脂Ｂ：タフマー ＤＦ１４０（三井化学株式会社製、商品名、密度＝０．９０５ｇ／ｃｍ３）
[Ultra low density polyethylene]
Resin B: TAFMER DF140 (Mitsui Chemicals, trade name, density = 0.905 g / cm 3 )
［炭酸カルシウム］
充填剤Ａ：ソフトン１０００（備北粉化工業株式会社製、商品名）
[Calcium carbonate]
Filler A: Softon 1000 (Bihoku Powder Chemical Co., Ltd., trade name)
［二酸化チタン］
充填剤Ｂ：タイペークＣＲ−６０−２（石原産業株式会社製、商品名）
[titanium dioxide]
Filler B: Taipei CR-60-2 (Ishihara Sangyo Co., Ltd., trade name)
発泡剤：ビニホールＡＣ＃３Ｃ−Ｋ２（永和化成工業株式会社製、商品名、アゾジカルボンアミド系発泡剤） Foaming agent: VINYHALL AC # 3C-K2 (manufactured by Eiwa Kasei Kogyo Co., Ltd., trade name, azodicarbonamide foaming agent)
発泡助剤Ａ：ＺＳ−６（日東化成工業株式会社製、商品名、１２−ヒドロキシステアリン酸亜鉛）
発泡助剤Ｂ：アデカスタブ ＯＦ−１０１（株式会社ＡＤＥＫＡ製、商品名、ステアリン酸亜鉛等脂肪酸金属塩及び炭酸カルシウムの重量比１：１混合物）
Foaming aid A: ZS-6 (Nitto Kasei Kogyo Co., Ltd., trade name, zinc 12-hydroxystearate)
Foaming aid B: ADK STAB OF-101 (manufactured by ADEKA Corporation, trade name, 1: 1 mixture by weight of fatty acid metal salt such as zinc stearate and calcium carbonate)
多価アルコールＡ：ノイライザーＰ（日本合成化学工業株式会社製、商品名、ペンタエリスリトール）
多価アルコールＢ：リケマールＳ−３００Ｗ（理研ビタミン株式会社製、商品名、ソルビタンモノステアレート）
Polyhydric alcohol A: Neulizer P (made by Nippon Synthetic Chemical Industry Co., Ltd., trade name, pentaerythritol)
Polyhydric alcohol B: Riquemar S-300W (Riken Vitamin Co., Ltd., trade name, sorbitan monostearate)
セル調整剤：ＨＰ−１０（株式会社ＡＤＥＫＡ製、商品名、亜リン酸エステル系酸化防止剤） Cell regulator: HP-10 (made by ADEKA Corporation, trade name, phosphite antioxidant)
安定剤：ＡＯ−５０（株式会社ＡＤＥＫＡ製、商品名、フェノール系酸化防止剤） Stabilizer: AO-50 (trade name, phenolic antioxidant manufactured by ADEKA Corporation)
滑剤：アデカスタブＡＰ−５４６（株式会社ＡＤＥＫＡ製、商品名） Lubricant: ADK STAB AP-546 (trade name, manufactured by ADEKA Corporation)
［発泡壁紙の評価］
作製した発泡壁紙について、下記の方法に従い、発泡倍率、インキの密着性及び変色を評価した。
[Evaluation of foam wallpaper]
The foamed wallpaper thus produced was evaluated for foaming magnification, ink adhesion, and discoloration according to the following methods.
（発泡倍率）
発泡前の乾燥発泡樹脂層の厚さ（ａ）を測定し、これを初期値とした。次に発泡炉にて発泡した後の発泡壁紙の発泡樹脂層の厚さ（ｂ）を測定し、（ｂ）／（ａ）を発泡倍率として算出した。結果を表２に示す。
(Foaming ratio)
The thickness (a) of the dried foamed resin layer before foaming was measured and used as the initial value. Next, the thickness (b) of the foamed resin layer of the foamed wallpaper after foaming in the foaming furnace was measured, and (b) / (a) was calculated as the foaming ratio. The results are shown in Table 2.
（インキ密着性）
織物絵柄を印刷した積層シートに対して、テープ（ニチバン株式会社製、ＣＴ−２４）による絵柄層の密着試験を行った。密着性に関しては、試験前と比較して絵柄層が９９％以上残留しているものを「◎」、絵柄層の残留率が５０％以上９９％未満のものを「○」、５０％未満のものを「×」とした。結果を表２に示す。
(Ink adhesion)
The adhesion test of the picture layer by a tape (Nichiban Co., Ltd., CT-24) was performed on the laminated sheet on which the textile pattern was printed. Regarding adhesion, “◎” indicates that the pattern layer remains 99% or more compared to before the test, and “○” indicates that the residual rate of the pattern layer is 50% or more and less than 99%, and indicates less than 50%. The thing was made into "x". The results are shown in Table 2.
（変色）
発泡後の発泡壁紙の色調を目視にて評価した。変色に関しては、比較例１の発泡壁紙と比較して差異がみられないものを「◎」、ほとんど黄変がみられないものを「○」、黄変しているものを「×」とした。結果を表２に示す。
(discoloration)
The color tone of the foamed wallpaper after foaming was visually evaluated. Regarding discoloration, “◎” indicates that there is no difference compared to the foamed wallpaper of Comparative Example 1, “○” indicates that yellowing is hardly observed, and “×” indicates that yellowing is not observed. . The results are shown in Table 2.
［積層シートの評価］
上記と同様にして、実施例１〜４、比較例１〜３の積層シートをそれぞれ得た。これらの積層シートについて、下記の方法に従い、コロナ処理後の濡れ性及びインキに対する接触角を評価した。結果を表２に示す。
[Evaluation of laminated sheet]
In the same manner as described above, laminated sheets of Examples 1 to 4 and Comparative Examples 1 to 3 were obtained. About these laminated sheets, according to the following method, the wettability after a corona treatment and the contact angle with respect to ink were evaluated. The results are shown in Table 2.
（濡れ性）
積層シートの樹脂シート側表面にコロナ放電処理を施した。コロナ放電処理した面に対し、濡れ張力試験用混合液（株式会社和光純薬製、ぬれ張力試験用混合液Ｎｏ．３０〜Ｎｏ．４２）を用いて、ＪＩＳ Ｋ６７６８に記載のとおり試験を行い、樹脂シートのぬれ張力（ｍＮ／ｍ＝Ｎ／ｍｍ）を測定した。
(Wettability)
Corona discharge treatment was applied to the resin sheet side surface of the laminated sheet. The surface subjected to the corona discharge treatment was tested as described in JIS K6768 using a mixed liquid for wet tension test (manufactured by Wako Pure Chemical Industries, Ltd., mixed liquid for wet tension test No. 30 to No. 42), The wetting tension (mN / m = N / mm) of the resin sheet was measured.
（接触角）
接触角の測定は株式会社マツボー製携帯式接触角計ＰＧ−３を用いて、ハイドリックインキ（大日精化工業株式会社製、ハイドリックＷＰ）に対する接触角を測定した。
(Contact angle)
The contact angle was measured using a portable contact angle meter PG-3 manufactured by Matsubo Co., Ltd., and the contact angle with respect to hydric ink (manufactured by Dainichi Seika Kogyo Co., Ltd., Hydrick WP).
実施例１〜５で作製された樹脂シートは良好な発泡性を有し且つ十分な印刷適性を有するとともに発泡過程での変色が発生しにくいことが確認された。 It was confirmed that the resin sheets produced in Examples 1 to 5 have good foamability and sufficient printability and are less likely to discolor during the foaming process.
Claims (11)
充填剤と、発泡剤と、発泡助剤と、樹脂分と、多価アルコールと、を含み、
前記発泡助剤が、１２−ヒドロキシステアリン酸亜鉛を含む、樹脂組成物。 A resin composition for forming the foamed resin layer of a foam wallpaper comprising a base material and a foamed resin layer provided on the base material,
Including a filler, a foaming agent, a foaming aid, a resin component, and a polyhydric alcohol,
The resin composition in which the said foaming adjuvant contains 12-hydroxy zinc stearate .
請求項９に記載の積層シートにおける前記樹脂シートに含まれる発泡剤を発泡させて得られる、発泡壁紙。 A foam wallpaper comprising a base material and a foamed resin layer provided on the base material,
A foamed wallpaper obtained by foaming a foaming agent contained in the resin sheet in the laminated sheet according to claim 9.
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| JPS5714628A (en) * | 1980-06-30 | 1982-01-25 | Showa Denko Kk | Resin composition |
| JP4733797B2 (en) * | 1997-10-30 | 2011-07-27 | 太陽化学株式会社 | Foamable vinyl chloride resin composition |
| JP3618993B2 (en) * | 1997-12-26 | 2005-02-09 | 株式会社カネカ | Composition for vinyl chloride foam |
| JP3886245B2 (en) * | 1998-03-20 | 2007-02-28 | 株式会社Ａｄｅｋａ | Foam material composition |
| JP3002673B1 (en) * | 1998-10-15 | 2000-01-24 | 昭島化学工業株式会社 | Foamable vinyl chloride resin composition |
| JP2004059608A (en) * | 2002-07-25 | 2004-02-26 | Mitsui Chemicals Inc | Aliphatic polyester foamed sheet |
| JP4984980B2 (en) * | 2007-03-07 | 2012-07-25 | 大日本印刷株式会社 | Decorative sheet |
| JP4946942B2 (en) * | 2008-03-28 | 2012-06-06 | 大日本印刷株式会社 | Foam wallpaper |
| JP5699319B2 (en) * | 2010-09-16 | 2015-04-08 | 大日本印刷株式会社 | Foam laminated sheet |
| JP5360280B1 (en) * | 2012-09-27 | 2013-12-04 | 大日本印刷株式会社 | Foam laminated sheet |
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