JP6733130B2 - Method for producing foamed wallpaper and method for producing laminated sheet - Google Patents
Method for producing foamed wallpaper and method for producing laminated sheet Download PDFInfo
- Publication number
- JP6733130B2 JP6733130B2 JP2015012101A JP2015012101A JP6733130B2 JP 6733130 B2 JP6733130 B2 JP 6733130B2 JP 2015012101 A JP2015012101 A JP 2015012101A JP 2015012101 A JP2015012101 A JP 2015012101A JP 6733130 B2 JP6733130 B2 JP 6733130B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- laminated sheet
- sheet
- producing
- base material
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 229920005989 resin Polymers 0.000 claims description 134
- 239000011347 resin Substances 0.000 claims description 134
- 239000002243 precursor Substances 0.000 claims description 52
- 229910000077 silane Inorganic materials 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 38
- 239000011342 resin composition Substances 0.000 claims description 36
- 239000004088 foaming agent Substances 0.000 claims description 33
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 30
- 238000005187 foaming Methods 0.000 claims description 23
- 238000010894 electron beam technology Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 14
- 229920005672 polyolefin resin Polymers 0.000 claims description 12
- 229920001684 low density polyethylene Polymers 0.000 claims description 11
- 239000004702 low-density polyethylene Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims 2
- 150000002736 metal compounds Chemical class 0.000 description 34
- 238000000034 method Methods 0.000 description 31
- 238000004132 cross linking Methods 0.000 description 28
- -1 polypropylene Polymers 0.000 description 28
- 238000001125 extrusion Methods 0.000 description 20
- 239000010410 layer Substances 0.000 description 19
- 238000011282 treatment Methods 0.000 description 18
- 238000000465 moulding Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 239000006260 foam Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000004383 yellowing Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000020169 heat generation Effects 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 6
- 229920003355 Novatec® Polymers 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 5
- 235000005822 corn Nutrition 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 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 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 239000004156 Azodicarbonamide Substances 0.000 description 3
- 150000008431 aliphatic amides Chemical class 0.000 description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 3
- 235000019399 azodicarbonamide Nutrition 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010943 off-gassing Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 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
- 239000005639 Lauric acid Substances 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000036284 oxygen consumption Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-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
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical class OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GBTKXRHCGMUSDA-UHFFFAOYSA-N [SiH3]OC(=O)CCC=C Chemical compound [SiH3]OC(=O)CCC=C GBTKXRHCGMUSDA-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- AYIGWTYMCHDVTN-UHFFFAOYSA-N [dicarboxy(ethenyl)silyl]formic acid Chemical compound OC(=O)[Si](C=C)(C(O)=O)C(O)=O AYIGWTYMCHDVTN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 description 1
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 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
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- PWOZXQOZUNMWKG-UHFFFAOYSA-N ethenyl(tripentoxy)silane Chemical compound CCCCCO[Si](OCCCCC)(OCCCCC)C=C PWOZXQOZUNMWKG-UHFFFAOYSA-N 0.000 description 1
- FEHYCIQPPPQNMI-UHFFFAOYSA-N ethenyl(triphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(C=C)OC1=CC=CC=C1 FEHYCIQPPPQNMI-UHFFFAOYSA-N 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 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
- 235000013312 flour Nutrition 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920005679 linear ultra low density polyethylene Polymers 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
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-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
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 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
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000009840 oxygen flask method Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 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
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane 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
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
本発明は、発泡壁紙の製造方法及び積層シートの製造方法に関する。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の製造方法及び積層シートの製造方法に関する。 The present invention relates to a method for manufacturing a foamed wallpaper and a method for manufacturing a laminated sheet. More specifically, the present invention relates to a method for producing a foamed wallpaper and a method for producing a laminated sheet, which can be used for wall decoration of buildings such as detached houses, apartment houses, shops and office buildings.
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用いられている。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いる（例えば、下記特許文献１及び２を参照。）。 As a wallpaper used for wall decoration of buildings, a 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 (see, for example, Patent Documents 1 and 2 below).
これらの発泡壁紙の製造方法としては、先ず、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、又は別途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る。その後、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。これらの方法は、基材上に樹脂組成物を塗布・乾燥する方法に比べて生産効率の点で有利である。 As a method for producing these foamed wallpaper, first, a resin composition containing a foaming agent is melt-extrusion coated and laminated on a substrate, or sheeting is separately performed by a T-die extrusion method, and then dry lamination or By laminating the base materials by thermal lamination, a laminated sheet having a resin sheet provided on the base materials is obtained. Then, if necessary, the resin sheet having the surface printed thereon is heated to decompose and foam the foaming agent. These methods are advantageous in production efficiency as compared with the method of coating and drying the resin composition on the substrate.
しかし、押出製膜では、スクリューを使って樹脂を溶融させる際に、せん断発熱によって樹脂温度が上昇してしまい、押出機内部で発泡剤の分解が発生しやすいという問題がある。エチレン−酢酸ビニル共重合体を用いる場合、押出機の腐食、極性化合物と無機充填剤との組合せによる過剰な増粘などが更に懸念される。 However, in extrusion film formation, when the resin is melted using a screw, the resin temperature rises due to shearing heat generation, and there is a problem that decomposition of the foaming agent easily occurs inside the extruder. When the ethylene-vinyl acetate copolymer is used, there is further concern about corrosion of the extruder and excessive thickening due to the combination of the polar compound and the inorganic filler.
これらの対策として、低溶融粘度の樹脂を使用することで、押出機内でのせん断発熱を抑える方法がある。しかし、一方で、発泡壁紙用の樹脂組成物は、製膜した樹脂シートが、発泡させたときに十分な発泡倍率が得られ、なおかつガス抜けが目立たない良好な発泡状態となるものであることが求められる。そのため、この場合には、製膜後に電子線等で架橋処理を行うことで、発泡に適する粘度に調整することが必要とされる。しかし、電子線照射においては、紙基材を黄変させてしまう等の基材への影響が少なくない。 As a countermeasure against these, there is a method of suppressing shear heat generation in the extruder by using a resin having a low melt viscosity. However, on the other hand, the resin composition for foamed wallpaper is such that the resin sheet formed into a film has a sufficient expansion ratio when foamed, and is in a good foaming state in which outgassing is not noticeable. Is required. Therefore, in this case, it is necessary to adjust the viscosity suitable for foaming by performing a crosslinking treatment with an electron beam or the like after the film formation. However, in the electron beam irradiation, there are many effects on the base material such as yellowing of the paper base material.
本発明は、上記事情に鑑みてなされたものであり、黄変等の品質劣化が十分に抑制された基材を備えつつ、発泡させたときに十分な発泡倍率とガス抜けが目立たない良好な発泡状態とを両立できる積層シートの製造方法及び発泡壁紙の製造方法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 includes a base material in which quality deterioration such as yellowing is sufficiently suppressed, and when foamed, a sufficient expansion ratio and outgassing are not noticeable. An object of the present invention is to provide a method for producing a laminated sheet and a method for producing a foamed wallpaper, which are compatible with a foamed state.
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製造方法であって、発泡剤と、シラン架橋性樹脂と、水和金属化合物と、を含む樹脂組成物を製膜して得られる樹脂シート前駆体を基材上にラミネートして積層シート前駆体を得る工程と、積層シート前駆体における樹脂シート前駆体を電子線の照射により樹脂シートとし、基材上に樹脂シートが設けられた積層シートを得る工程と、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て発泡樹脂層を形成する工程と、を備える、発泡壁紙の製造方法を提供する。 That is, the present invention is a method for producing a foamed wallpaper comprising a base material and a foamed resin layer provided on the base material, wherein a foaming agent, a silane crosslinkable resin, and a hydrated metal compound, A step of obtaining a laminated sheet precursor by laminating a resin sheet precursor obtained by forming a film of a resin composition containing a resin sheet precursor by irradiating an electron beam on the resin sheet precursor in the laminated sheet precursor. And a step of obtaining a laminated sheet in which a resin sheet is provided on a base material, and a step of foaming a foaming agent contained in the resin sheet in the laminated sheet to form a foamed resin layer. I will provide a.
本発明によれば、黄変等の品質劣化が十分に抑制された基材上に、十分な発泡倍率と良好な発泡状態とを有する発泡樹脂層が設けられた発泡壁紙を製造することができる。 According to the present invention, it is possible to produce a foamed wallpaper in which a foamed resin layer having a sufficient expansion ratio and a good foaming state is provided on a base material on which quality deterioration such as yellowing is sufficiently suppressed. ..
このような効果が得られる理由として、シラン架橋性樹脂と水和金属化合物とを組み合わせて用いることにより、発泡剤を発泡させる際に、水和金属化合物が加熱されることで、脱水反応が起こり、シラン架橋反応の効率が高められたことが考えられる。これにより、押出製膜に適した低溶融粘度の樹脂を用いる場合であっても、基材への影響が少ない電子線照射量で、発泡セルが微細かつ均一になり、十分な発泡倍率と良好な発泡状態とを両立できたものと本発明者らは推察する。 As a reason why such an effect is obtained, by using a silane crosslinkable resin and a hydrated metal compound in combination, the hydrated metal compound is heated when the foaming agent is foamed, so that a dehydration reaction occurs. It is considered that the efficiency of the silane crosslinking reaction was increased. As a result, even when a resin with a low melt viscosity suitable for extrusion film formation is used, the foam cells become fine and uniform with a small amount of electron beam irradiation that does not affect the substrate, and a sufficient expansion ratio and good The present inventors presume that it was possible to achieve both excellent foaming state.
また、本発明の製造方法により得られた発泡壁紙は、圧縮回復性やコーンカロリー燃焼性試験において優れた性能を有することが可能となる。なお、このような効果が得られることも水和金属化合物の脱水反応によるものと本発明者らは考えている。 In addition, the foamed wallpaper obtained by the production method of the present invention can have excellent performance in compression recovery and corn calorie burning test. The present inventors believe that such an effect can be obtained by the dehydration reaction of the hydrated metal compound.
本発明に係る発泡壁紙の製造方法において、上記樹脂組成物は、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更に含むことができる。このような無極性の樹脂を使用することで、二酸化チタン又は炭酸カルシウム等の各種充填剤を添加した際の増粘効果を最小限に抑えることができる。増粘効果を最小限に抑えることで、ドローレゾナンスが向上して製膜安定性が高まるとともに、押出機内でのスクリュー回転トルクの過上昇や樹脂圧力を抑制でき、同時にせん断による樹脂の発熱を最小限に抑えることも可能となる。 In the method for producing a foamed wallpaper according to the present invention, the resin composition may further include an ethylene homopolymer or a copolymer of ethylene and another olefin. By using such a non-polar resin, the thickening effect when various fillers such as titanium dioxide or calcium carbonate are added can be minimized. By minimizing the thickening effect, the draw resonance is improved and the film-forming stability is improved, while the screw rotation torque in the extruder and the resin pressure can be suppressed, and at the same time the resin heat generation due to shearing is minimized. It is also possible to limit it.
本発明に係る発泡壁紙の製造方法において、上記水和金属化合物は、水酸化アルミニウムを含むことが好ましい。水酸化アルミニウムは、水酸化マグネシウム等に比べて脱水反応の開始温度が低いため、より低温でシラン架橋反応を促進することができる。これにより、より低温からシラン架橋反応が進行するため、発泡壁紙の表面がより平滑になり、かつセルサイズがより微細で均一になる。 In the method for producing a foamed wallpaper according to the present invention, the hydrated metal compound preferably contains aluminum hydroxide. Since aluminum hydroxide has a lower starting temperature for the dehydration reaction than magnesium hydroxide or the like, it can accelerate the silane crosslinking reaction at a lower temperature. As a result, the silane crosslinking reaction proceeds from a lower temperature, so that the surface of the foamed wallpaper becomes smoother and the cell size becomes finer and uniform.
本発明に係る発泡壁紙の製造方法において、上記水和金属化合物の平均粒径は、５μｍ以下であることが好ましい。粒径を小さくすることにより、表面積が増加し、一度に大量の水分を脱水させることができる。これにより、シラン架橋反応を促進できる水分量をより少ない水和金属化合物によって増加させることができ、より効率的に架橋を行うことができる。 In the method for producing a foamed wallpaper according to the present invention, the hydrated metal compound preferably has an average particle size of 5 μm or less. By reducing the particle size, the surface area is increased and a large amount of water can be dehydrated at once. Thereby, the amount of water capable of promoting the silane crosslinking reaction can be increased by a smaller amount of the hydrated metal compound, and the crosslinking can be performed more efficiently.
また、本発明は、基材と、該基材上に設けられた樹脂シートと、を備える積層シートの製造方法であって、発泡剤と、シラン架橋性樹脂と、水和金属化合物と、を含む樹脂組成物を製膜して得られる樹脂シート前駆体を基材上にラミネートして積層シート前駆体を得る工程と、積層シート前駆体における樹脂シート前駆体を電子線の照射により樹脂シートとし、基材上に樹脂シートが設けられた積層シートを得る工程と、を備える、積層シートの製造方法を提供する。 Further, the present invention is a method for producing a laminated sheet comprising a base material and a resin sheet provided on the base material, wherein a foaming agent, a silane crosslinkable resin, and a hydrated metal compound are included. A step of obtaining a laminated sheet precursor by laminating a resin sheet precursor obtained by forming a film of a resin composition containing the resin sheet precursor in the laminated sheet precursor into a resin sheet by electron beam irradiation. And a step of obtaining a laminated sheet in which a resin sheet is provided on a base material.
本発明の積層シートの製造方法によれば、黄変等の品質劣化が十分に抑制された基材を備えつつ、発泡させたときに十分な発泡倍率とガス抜けが目立たない良好な発泡状態とを両立できる積層シートを製造することができる。 According to the method for producing a laminated sheet of the present invention, while providing a base material in which quality deterioration such as yellowing is sufficiently suppressed, a sufficient foaming ratio and a good foaming state in which degassing is not noticeable when foamed. It is possible to produce a laminated sheet that can satisfy both requirements.
本発明に係る発積層シートの製造方法において、上記樹脂組成物は、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更に含むことができる。 In the method for producing a laminated laminate sheet according to the present invention, the resin composition may further include an ethylene homopolymer or a copolymer of ethylene and another olefin.
本発明に係る発積層シートの製造方法において、上記水和金属化合物は、水酸化アルミニウムを含むことが好ましい。 In the method for producing a laminated laminate sheet according to the present invention, the hydrated metal compound preferably contains aluminum hydroxide.
本発明に係る発積層シートの製造方法において、上記水和金属化合物の平均粒径は、５μｍ以下であることが好ましい。 In the method for producing a laminated foam sheet according to the present invention, the average particle size of the hydrated metal compound is preferably 5 μm or less.
本発明によれば、黄変等の品質劣化が十分に抑制された基材を備えつつ、発泡させたときに十分な発泡倍率とガス抜けが目立たない良好な発泡状態とを両立できる積層シート及び発泡壁紙の製造方法を提供することができる。 According to the present invention, a laminated sheet having a base material in which quality deterioration such as yellowing is sufficiently suppressed, and having both a sufficient expansion ratio when foamed and a good foaming state in which outgassing is inconspicuous, and A method for manufacturing a foamed wallpaper can be provided.
本実施形態に係る積層シートは、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を製造するために用いられる積層シートであって、基材と該基材上に設けられ、発泡により発泡樹脂層を形成できる樹脂シートとを備える。 The laminated sheet according to the present embodiment is a laminated sheet used for producing a foamed wallpaper including a base material and a foamed resin layer provided on the base material, and provided on the base material and the base material. And a resin sheet capable of forming a foamed resin layer by foaming.
［積層シートの製造方法］
本実施形態に係る積層シートの製造方法は、樹脂組成物を製膜して得られる樹脂シート前駆体を基材上にラミネートして積層シート前駆体を得る工程と、積層シート前駆体における樹脂シート前駆体を電子線の照射により樹脂シートとし、基材上に樹脂シートが設けられた積層シートを得る工程と、を備える。
[Manufacturing method of laminated sheet]
The method for producing a laminated sheet according to the present embodiment includes a step of obtaining a laminated sheet precursor by laminating a resin sheet precursor obtained by forming a resin composition on a substrate, and a resin sheet in the laminated sheet precursor. Forming a resin sheet by irradiating the precursor with an electron beam to obtain a laminated sheet in which the resin sheet is provided on a base material.
本実施形態に係る樹脂組成物は、発泡剤と、シラン架橋性樹脂と、水和金属化合物と、を含む。 The resin composition according to the present embodiment contains a foaming agent, a silane crosslinkable resin, and a hydrated metal compound.
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、ベンゼンスルホニルヒドラジド、ｐ−トルエンスルホニルヒドラジド等のヒドラジド系発泡剤、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。上記の発泡剤の中でも、毒性が少なく、発泡開始温度の調節が容易で適用範囲が広く、なおかつ分解温度が比較的高く、後述する水和金属化合物の脱水温度において発泡しにくいことから、ＡＤＣＡが好ましい。 As the foaming agent according to this embodiment, for example, a pyrolytic foaming agent can be used. Examples of the thermal decomposition type foaming agent include azo type foaming agents such as azodicarbonamide (ADCA), azobutyronitrile and diazoaminobenzene, hydrazide type foaming agents such as benzenesulfonyl hydrazide and p-toluenesulfonyl hydrazide, N, Examples thereof include nitroso-based foaming agents such as N'-dinitrosopentamethylenetetramine. These may be used alone or in combination of two or more. Among the above-mentioned foaming agents, ADCA is less toxic, the foaming start temperature can be easily adjusted and the applicable range is wide, and the decomposition temperature is relatively high, and it is difficult to foam at the dehydration temperature of the hydrated metal compound described later. preferable.
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。 The content of the foaming agent is not particularly limited, but its total amount is preferably 1 to 20% by mass based on the total amount of the resin composition. 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.
本実施形態に係る樹脂組成物は、樹脂分としてシラン架橋性樹脂を含む。シラン架橋性樹脂としては、加水分解性シリル基を有する樹脂が挙げられ、例えばシラン架橋性ポリオレフィン系樹脂等を用いることができる。シラン架橋性ポリオレフィン系樹脂としては、母体としてのポリオレフィン系重合体に加水分解性シリル基を主として側鎖に導入した樹脂が挙げられる。このような樹脂としては、低密度ポリエチレン系、高密度ポリエチレン系、エチレン−酢酸ビニル共重合体系、ポリプロピレン系等の重合体に加水分解性シリル基を主として側鎖に導入した樹脂が挙げられる。架橋は、置換シリル基の加水分解により行われる。なお、このシリル基が末端に位置するポリオレフィン系樹脂が含まれていてもよい。 The resin composition according to the present embodiment contains a silane crosslinkable resin as a resin component. Examples of the silane crosslinkable resin include a resin having a hydrolyzable silyl group, and for example, a silane crosslinkable polyolefin resin or the like can be used. Examples of the silane crosslinkable polyolefin-based resin include a resin in which a hydrolyzable silyl group is mainly introduced into a side chain of a polyolefin-based polymer as a matrix. Examples of such a resin include a low density polyethylene type, a high density polyethylene type, an ethylene-vinyl acetate copolymer type, and a polypropylene type polymer in which a hydrolyzable silyl group is mainly introduced into a side chain. Crosslinking is performed by hydrolysis of the substituted silyl group. It should be noted that a polyolefin-based resin having this silyl group at the terminal may be included.
シラン架橋性ポリオレフィン系樹脂は、ポリオレフィン系重合体を構成するモノマーとエチレン性不飽和基又はエポキシ基を有するシラン化合物とを容器中でランダム共重合させる方法、又はポリオレフィン系重合体の溶融物に過酸化物を用いてエチレン性不飽和基又はエポキシ基を有するシラン化合物をグラフト共重合する方法等により得ることができる。ここで、母体としてのポリオレフィン系重合体は、上記の樹脂のうちの１種を単独で又は２種以上を組み合わせて用いることができる。さらに、母体のポリオレフィン系樹脂は、樹脂同士の混合又は分解が許容される程度であれば、上記ポリオレフィン系樹脂と、上記ポリオレフィン系樹脂とは異なる樹脂とを併用してもよい。混合又は分散の程度は、使用する押出機の種類により大差があり、また適宜の相溶化剤も使用できるので、組合せ樹脂は一概に区分はできないが、同種の樹脂であることが好ましい。エチレン性不飽和基を有するシラン化合物としては、例えば、ビニル基を有するシラン化合物、アクリロイル基を有するシラン化合物、メタクリロイル基を有するシラン化合物等が挙げられる。ビニル基を有するシラン化合物としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルトリイソプロポキシシラン、ビニルトリブトキシシラン、ビニルトリペンチロキシシラン、ビニルトリフェノキシシラン、ビニルトリベンジルオキシシラン、ビニルトリメチレンジオキシシラン、ビニルトリエチレンジオキシシラン、ビニルプロピオニルオキシシラン、ビニルトリアセトキシシラン、及びビニルトリカルボキシシラン等が挙げられる。アクリロイル基を有するシラン化合物としては、３−アクリロキシプロピルトリメトキシシラン等が挙げられる。メタクリロイル基を有するシラン化合物としては、３−メタクリロキシプロピルメチルジメトキシシラン等が挙げられる。
エポキシ基を有するシラン化合物としては、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン等が挙げられる。
The silane crosslinkable polyolefin resin is a method of randomly copolymerizing a monomer constituting the polyolefin polymer and a silane compound having an ethylenically unsaturated group or an epoxy group in a container, or a polyolefin polymer melt It can be obtained by a method of graft-copolymerizing a silane compound having an ethylenically unsaturated group or an epoxy group using an oxide. Here, the polyolefin-based polymer as the matrix can be used alone or in combination of two or more of the above resins. Further, as the base polyolefin-based resin, the above-mentioned polyolefin-based resin and a resin different from the above-mentioned polyolefin-based resin may be used in combination as long as mixing or decomposition of the resins is allowed. The degree of mixing or dispersion varies greatly depending on the type of extruder used, and an appropriate compatibilizer can also be used. Therefore, the combined resins cannot be unconditionally categorized, but the same type of resin is preferable. Examples of the silane compound having an ethylenically unsaturated group include a silane compound having a vinyl group, a silane compound having an acryloyl group, and a silane compound having a methacryloyl group. Examples of the silane compound having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentyloxysilane, vinyltriphenoxysilane, vinyltribenzyloxy. Examples thereof include silane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane. Examples of the silane compound having an acryloyl group include 3-acryloxypropyltrimethoxysilane. Examples of the silane compound having a methacryloyl group include 3-methacryloxypropylmethyldimethoxysilane.
Examples of the silane compound having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane.
シラン架橋性樹脂は市販品を用いることができ、例えば、三菱化学株式会社製「リンクロン」等を用いることができる。 As the silane crosslinkable resin, a commercially available product can be used, and for example, “LINKLON” manufactured by Mitsubishi Chemical Corporation can be used.
本実施形態に係る樹脂組成物におけるシラン架橋性樹脂の含有量は、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く、３〜１０質量％であることがより好ましい。 The content of the silane crosslinkable resin in the resin composition according to the present embodiment is preferably 1 to 20% by mass, more preferably 3 to 10% by mass, based on the total amount of the resin composition.
樹脂分は、上述したシラン架橋性樹脂以外の樹脂を含んでいてもよい。このような樹脂としては、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）、スチレン系樹脂（ポリスチレン、アクリロニトリル・スチレン樹脂、アクリロニトリル・ブタジエン・スチレン樹脂等）、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 may contain a resin other than the silane crosslinkable resin described above. Such a resin preferably contains a chlorine-free thermoplastic resin from the viewpoint of preventing the generation of toxic gases such as dioxins during combustion. Examples of the non-chlorine thermoplastic resin include ethylene homopolymers, copolymers of ethylene and other olefins, polyolefin resins (polypropylene, polybutene, polymethylpentene, etc.), styrene resins (polystyrene, acrylonitrile/styrene resin). , Acrylonitrile/butadiene/styrene resin, etc., ethylene copolymer (ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer) Polymers, ethylene-methacrylic acid copolymers, etc.) and the like. These may be used alone or in combination of two or more.
中でも、本実施形態に係る非塩素系熱可塑性樹脂は、無極性であることが好ましい。このような無極性の非塩素系熱可塑性樹脂を用いることで、下記で述べる充填剤を添加した際の増粘効果を最小限に抑えることができ、高品質の壁紙を安定して生産することができる。また、このような無極性の非塩素系熱可塑性樹脂は、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できる。本実施形態においては、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用いた場合であっても、上記シラン架橋性樹脂と水和金属化合物との組合せにより、コーンカロリー難燃性試験における性能を十分に確保することができる。 Among them, the non-chlorine thermoplastic resin according to this embodiment is preferably non-polar. By using such non-polar non-chlorine type thermoplastic resin, it is possible to minimize the thickening effect when the filler described below is added, and to stably produce high quality wallpaper. You can Further, such a non-polar non-chlorine type thermoplastic resin may contain an ethylene homopolymer or a copolymer of ethylene and another olefin. In the present embodiment, even when an ethylene homopolymer or a copolymer of ethylene and another olefin is used, due to the combination of the silane crosslinkable resin and the hydrated metal compound, the corn calorie flame retardancy is obtained. The performance in the test can be sufficiently secured.
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 the high pressure method and high density polyethylene containing no comonomer synthesized by the medium and low pressure method. Of these, low density polyethylene is preferable.
低密度ポリエチレンは、例えば、密度が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０．９１ｇ／ｃｍ３以上０．９３ｇ／ｃｍ３以下であり、より好ましくは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℃〜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１０〜２００のものが好ましく、１０〜１００のものがより好ましい。ＭＦＲが１０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ことを抑制することができる。一方、ＭＦＲが２００以下であれば、効率的に発泡させることができ、発泡樹脂層の圧縮回復性等の機械強度が保たれ、発泡壁紙の施工性及び耐久性をより向上させることができる。 Low density polyethylene, for example, those having a density in the range of 0.91 g / cm 3 or more 0.94 g / cm 3 or less. The density of low-density polyethylene is preferably not 0.91 g / cm 3 or more 0.93 g / cm 3 or less, more preferably 0.92 g / cm 3 or more 0.93 g / cm 3 or less. The molecular weight, melting point, melt flow rate (MFR), etc. 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. When the melting point is 140° C. or lower, it is not necessary to melt the resin at a higher temperature when molding the resin, and there is less possibility that the foaming agent will decompose during molding. On the other hand, when the melting point is 50° C. or higher, sufficient thermal durability in actual use can be obtained. The MFR is preferably 10 to 200, more preferably 10 to 100. When the MFR is 10 or more, shearing heat generated during molding can be suppressed, the processing temperature can be easily controlled, and decomposition of the foaming agent during molding can be suppressed. On the other hand, when the MFR is 200 or less, it is possible to efficiently foam, the mechanical strength such as compression recovery of the foamed resin layer is maintained, and the workability and durability of the foamed wallpaper can be further improved.
低密度ポリエチレンとしては、例えば、ノバテックＬＤ ＬＪ８０２Ａ、ノバテックＬＤ ＬＣ６０４、ノバテックＬＤ ＬＣ６００Ａ（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）、ペトロセン３５３（東ソー製）等の市販品を用いることができる。 As the low-density polyethylene, for example, commercially available products such as Novatec LD LJ802A, Novatec LD LC604, Novatec LD LC600A (above, made by Nippon Polyethylene), Ube Polyethylene J2516 (made by Ube Maruzen Polyethylene), Petrosen 353 (made by Tosoh), etc. should be used. You can
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。 Copolymers of ethylene and other olefins include, for example, linear low-density polyethylene, ultra-low-density polyethylene, and high-density polyethylene obtained by copolymerization with comonomers. These may be used alone. Or, two or more kinds can be used in combination. Among them, ultra low density polyethylene is preferable.
超低密度ポリエチレンとしては、例えば、密度が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０．８８ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下であり、より好ましくは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以上７０以下のものが好ましく、３以上７０未満のものがより好ましく、４以上６５以下のものが更に好ましい。ＭＦＲが３以上であれば、成型中に発泡剤が分解してしまうことを抑制することができる。一方、ＭＦＲが７０以下であれば、発泡樹脂層の機械強度が保たれ、発泡壁紙の施工性及び耐久性をより向上させることができる。 The ultra low density polyethylene, for example, those having a density in the range of less than 0.88 g / cm 3 or more 0.91 g / cm 3. The density of the ultra-low density polyethylene is preferably 0.88 g/cm 3 or more and 0.90 g/cm 3 or less, and more preferably 0.89 g/cm 3 or more and 0.90 g/cm 3 or less. 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°C to 140°C, more preferably 60°C to 110°C. When the melting point is 140° C. or lower, it is not necessary to melt the resin at a higher temperature when molding the resin, and there is less possibility that the foaming agent will decompose during molding. On the other hand, when the melting point is 50° C. or higher, sufficient thermal durability in actual use can be obtained. The MFR is preferably 3 or more and 70 or less, more preferably 3 or more and less than 70, still more preferably 4 or more and 65 or less. When the MFR is 3 or more, decomposition of the foaming agent during molding can be suppressed. On the other hand, when the MFR is 70 or less, the mechanical strength of the foamed resin layer is maintained, and the workability and durability of the foamed wallpaper can be further improved.
超低密度ポリエチレンとしては、例えば、タフマー ＤＦ１４０、ＤＦ９４０、ＤＦ７３５０（以上、いずれも三井化学製）、カーネル ＫＪ−６４０Ｔ（日本ポリエチレン製）、エクセレンＦＸ ＣＸ５５０８（住友化学製）、エンゲージ ８４００／８４０７（ダウ・ケミカル製）、エボリューＰ ＳＰ９０１００（プライムポリマー製）等の市販品を用いることができる。 Examples of ultra-low density polyethylene include Tuffmer DF140, DF940, DF7350 (all manufactured by Mitsui Chemicals), Kernel KJ-640T (manufactured by Nippon Polyethylene), Excellen FX CX5508 (manufactured by Sumitomo Chemical), Engage 8400/8407 (Dow). Commercially available products such as Chemicals) and Evolution P SP90100 (Prime Polymer) can be used.
本実施形態の樹脂組成物における樹脂分の総含有量は、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 content of the resin component in the resin composition of the present embodiment is preferably 20 to 80 mass%, more preferably 40 to 75 mass%, and more preferably 50 to 70, based on the total amount of the resin composition. More preferably, it is mass %. In this case, the resin component may be crosslinked.
本実施形態に係る樹脂分は塩素原子の含有量が０〜１０質量％であることが好ましく、０〜５質量％であることがより好ましい。特に本実施形態に係る樹脂分は、塩素原子を含まないことが更に好ましい。樹脂分における塩素原子の含有量の算出方法は、ＪＩＳ−Ｋ−７２２９記載の酸素フラスコ燃焼法の方法が挙げられる。 The resin component according to this embodiment preferably has a chlorine atom content of 0 to 10% by mass, and more preferably 0 to 5% by mass. In particular, it is more preferable that the resin component according to this embodiment does not contain a chlorine atom. Examples of the method for calculating the content of chlorine atoms in the resin component include the oxygen flask combustion method described in JIS-K-7229.
本実施形態に係る水和金属化合物とは、加熱により脱水する金属化合物をいう。このような水和金属化合物は、加熱により水分を放出することができる。水和金属化合物としては、例えば、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、水酸化マンガン、水酸化鉄、水酸化亜鉛、水酸化銅等が挙げられる。 The hydrated metal compound according to this embodiment refers to a metal compound that is dehydrated by heating. Such a hydrated metal compound can release water by heating. Examples of the hydrated metal compound include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, manganese hydroxide, iron hydroxide, zinc hydroxide, copper hydroxide and the like.
水和金属化合物は、粒子状であることが好ましい。水和金属化合物の平均粒径は、５μｍ以下であることが好ましく、３μｍ以下であることがより好ましい。水和金属化合物の平均粒径を５μｍ以下とすることにより、表面積が増加し、一度に大量の水分が脱水される。これにより、シラン架橋反応に用いられる水分量が多くなり、より効率的に架橋が行われる。また、水和金属化合物の平均粒径の下限値は、粘度の上昇を抑える観点から、０．０１μｍ以上であることが好ましく、０．１μｍ以上であることがより好ましい。水和金属化合物の平均粒径とは、粒度分布の中央値に相当する５０％平均粒径であり、例えば、市販の粒度分布測定装置を用いて測定することができる。 The hydrated metal compound is preferably in the form of particles. The average particle size of the hydrated metal compound is preferably 5 μm or less, more preferably 3 μm or less. By setting the average particle size of the hydrated metal compound to 5 μm or less, the surface area increases and a large amount of water is dehydrated at one time. As a result, the amount of water used in the silane crosslinking reaction increases, and crosslinking is performed more efficiently. Further, the lower limit of the average particle size of the hydrated metal compound is preferably 0.01 μm or more, and more preferably 0.1 μm or more, from the viewpoint of suppressing an increase in viscosity. The average particle size of the hydrated metal compound is a 50% average particle size corresponding to the median value of the particle size distribution, and can be measured using, for example, a commercially available particle size distribution measuring device.
水和金属化合物は、分散性、成形性、難燃性等の向上の観点から、各種の表面処理を施してもよい。このような表面処理を施した水和金属化合物としては、分散性及び成形性の向上の観点からは、例えば、硝酸陰イオン処理水酸化アルミニウム、高温熱水化処理水酸化アルミニウム等が挙げられ、難燃性の向上の観点からは、例えば、硝酸塩処理水酸化アルミニウム、錫酸亜鉛表面処理水酸化アルミニウム、ニッケル化合物表面処理水酸化マグネシウム等のほか、金雲母処理、シリコーン処理、シリコーンポリマー処理等の処理を施した水和金属化合物などが挙げられる。 The hydrated metal compound may be subjected to various surface treatments from the viewpoint of improving dispersibility, moldability, flame retardancy and the like. As the hydrated metal compound subjected to such a surface treatment, from the viewpoint of improving dispersibility and moldability, for example, nitrate anion treated aluminum hydroxide, high temperature hydrothermal treatment treated aluminum hydroxide, and the like, From the viewpoint of improving flame retardancy, for example, nitrate-treated aluminum hydroxide, zinc stannate surface-treated aluminum hydroxide, nickel compound surface-treated magnesium hydroxide, etc., as well as phlogopite treatment, silicone treatment, silicone polymer treatment, etc. Examples include treated hydrated metal compounds and the like.
本実施形態に係る樹脂組成物における水和金属化合物の含有量は、樹脂組成物全量を基準として、２０〜７０質量％であることが好ましく、２５〜６０質量％であることがより好ましい。水和金属化合物の含有量が２０質量％以上であれば、水和金属化合物から放出された水が効率的に架橋反応に寄与する傾向にあり、７０質量％以下であれば、成形加工の容易性を高めることができる。 The content of the hydrated metal compound in the resin composition according to the present embodiment is preferably 20 to 70% by mass, and more preferably 25 to 60% by mass, based on the total amount of the resin composition. If the content of the hydrated metal compound is 20% by mass or more, the water released from the hydrated metal compound tends to contribute to the crosslinking reaction efficiently, and if it is 70% by mass or less, the molding process is easy. You can improve your sex.
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。 Moreover, the resin composition according to the present embodiment may be colored by adding a pigment or the like, if necessary. The coloring by the addition of the 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 amount of the pigment added 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、充填剤、発泡助剤、水和金属化合物以外の難燃剤、セル調整剤、安定剤、滑剤、シラン架橋助剤等の周知の添加剤を用いることができる。 In addition, known additives such as fillers, foaming aids, flame retardants other than hydrated metal compounds, cell regulators, stabilizers, lubricants, silane crosslinking aids, etc. are used in the resin composition, if necessary. be able to.
充填剤としては、無機充填剤又は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、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。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、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。 Examples of the filler include an inorganic filler and an organic filler. Examples of the inorganic filler include calcium carbonate and titanium dioxide, and these can be used alone or in combination of two or more. Examples of the organic filler include melamine cyanurate, polytetrafluoroethylene (PTFE), wood flour, cellulose and derivatives thereof, and these may be used alone or in combination of two or more. it can.
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が、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かカロリーが低く、製造コストの手頃な発泡壁紙を製造することができる。 The content of the filler is not particularly limited, but the total amount thereof is preferably 10 to 60 mass% based on the total amount of the resin composition. Reasons for adding the filler include ensuring the concealing property of the foam wallpaper, reducing the calories burned per unit area, and reducing the manufacturing cost by increasing the bulk, but the inclusion of the filler (particularly the inorganic filler) When the amount is 20 to 40% by mass based on the total amount of the resin composition, it is possible to produce a foamed wallpaper which has a low burning or calorie while maintaining a good hiding property as a foamed wallpaper and which is low in manufacturing cost.
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族アミド系、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ほか、尿素系、塩化亜鉛、酸化亜鉛等が挙げられる。 Examples of the foaming aid include aliphatic stearic acid, lauric acid, and other aliphatic amides, stearic acid amide, oleic acid amide, and other aliphatic amides, and zinc stearate, calcium laurate, zinc octylate, and other fatty acid metal salt-based compounds. In addition, urea type, zinc chloride, zinc oxide and the like can be mentioned.
水和金属化合物以外の難燃剤としては、例えば、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 other than the hydrated metal compound include phosphoric acid flame retardants such as phosphoric acid ester flame retardants and brominated flame retardants such as tetrabromobisphenol A.
セル調整剤としては、例えば、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。 Examples of the cell adjusting agent include acrylic acid ester-based resins and methacrylic acid ester-based resins.
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補足剤、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。 Examples of the stabilizer include radical scavengers such as phenol/amine antioxidants, hindered amine light stabilizers, phosphorus decomposers such as phosphorus compounds and sulfur compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, and benzophenone compounds. Examples include UV 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族アミド系、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, aliphatic amide-based agents 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. Can be mentioned.
シラン架橋助剤としては、例えば、スズ系の架橋助剤等が挙げられる。 Examples of the silane crosslinking aid include tin-based crosslinking aids.
本実施形態の樹脂組成物においては、製膜した樹脂シートの架橋を効率的に行うために、トリメチルプロパン・トリメタクリレート、トリメチルプロパン・トリアクリレート、トリアリルイソシアヌレートなどの架橋助剤を含有することが好ましい。 In the resin composition of the present embodiment, in order to efficiently crosslink the resin sheet formed into a film, it is necessary to contain a crosslinking auxiliary agent such as trimethylpropane/trimethacrylate, trimethylpropane/triacrylate, and triallyl isocyanurate. Is preferred.
上記架橋助剤の配合量としては、樹脂成分１００質量部に対して、０．０１〜５質量部が好ましく、０．１〜１．０質量部がより好ましい。この範囲内であれば、架橋助剤の添加効果を十分に得ることができるとともに、樹脂シート表層へのブルーミングなどを防止しやすい。 The amount of the cross-linking aid compounded is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 1.0 part by mass, relative to 100 parts by mass of the resin component. Within this range, the effect of adding the crosslinking aid can be sufficiently obtained, and blooming to the surface layer of the resin sheet can be easily prevented.
本実施形態に係る樹脂シート前駆体は、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前駆体は、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。 The resin sheet precursor according to this embodiment is formed from the resin composition according to this embodiment. The resin sheet precursor 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前駆体は、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。 In addition to extrusion molding, the resin sheet precursor according to the present embodiment may be formed by known molding methods such as injection molding, press molding, blow molding, calendar molding, coating molding, cast molding, dipping molding, vacuum molding and transfer molding. It can be manufactured.
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 may be prepared by melting, kneading, and dispersing each component with an extruder, and then appropriately pelletizing the resin composition. The extruder may be a single-screw extruder or a twin-screw extruder, but a twin-screw extruder is preferable in consideration 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２ＭＰａ〜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、３ＭＰａ〜４０ＭＰａが好ましく、３ＭＰａ〜３０ＭＰａがより好ましい。 The conditions for the extrusion film formation include an extrusion temperature of 100° C. to 160° C. and an extrusion pressure of 2 MPa to 50 MPa. The extrusion temperature is preferably 110° C. to 150° C., and more preferably 120° C. to 140° C., from the viewpoint of suppressing the decomposition of the foaming agent component and at least the melting point of the polyethylene component. From the viewpoint of extrusion stability, the extrusion pressure is preferably 3 MPa to 40 MPa, more preferably 3 MPa to 30 MPa.
樹脂シート前駆体の厚みは、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５０μｍ〜２００μｍとすることができる。 The thickness of the resin sheet precursor can be appropriately set according to the application, but for example, in the case of use as a foam wallpaper, it can be set to 50 μm to 200 μm.
本実施形態に係る積層シート前駆体は、上記樹脂シート前駆体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、樹脂シート前駆体と基材とを、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、過熱蒸気によって樹脂シート前駆体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前駆体に転写されることを抑制することができる。また、樹脂シート前駆体がシラン架橋性樹脂を含む場合には、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。 The laminated sheet precursor according to this embodiment can be obtained by laminating the resin sheet precursor on a substrate. The method for laminating is not particularly limited, and examples include a method of thermocompression bonding the resin sheet precursor and the substrate using a hot press machine, a method of pressure bonding using superheated steam, and the like. To be According to the method of performing pressure bonding using superheated steam, it becomes possible to laminate on the base material while maintaining the molten state of the surface of the resin sheet precursor by the superheated steam, and by the leveling effect of the base material to be adhered. It is possible to prevent the unevenness of the surface from being transferred to the resin sheet precursor. Moreover, when the resin sheet precursor contains a silane crosslinkable resin, the silane crosslinkable resin can be efficiently crosslinked 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 above-mentioned base material is not particularly limited as long as it is one that has been usually used as a paper base material such as a conventional backing paper for wallpaper. As such a base material, 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 or magnesium hydroxide is used. Examples include mixed papers made of inorganic materials. These weighing may be a 50 to 300 g / m 2, it may be 60 to 160 / m 2.
また、基材と上記樹脂シート前駆体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前駆体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 adhesiveness between the base material and the resin sheet precursor, the surface of the base material on which the resin sheet precursor is provided has, for example, corona discharge treatment, plasma treatment, ozone treatment, or the like. It may be subjected to an easy adhesion treatment, or may be provided with an easy adhesion treatment layer formed of an acrylic-butyl copolymer, polyurethane composed of an isocyanate and a polyol, or the like.
本実施形態に係る積層シートは、上記積層シート前駆体における樹脂シート前駆体を、電子線の照射により架橋処理し、樹脂シートとすることで得ることができる。 The laminated sheet according to this embodiment can be obtained by subjecting the resin sheet precursor in the laminated sheet precursor to a crosslinking treatment by irradiation with an electron beam to form a resin sheet.
電子線の照射は、例えば、製膜した樹脂シート前駆体の片面側から、又は両面から電子線を照射することにより、樹脂シート前駆体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、樹脂シート前駆体の厚みにもよるが、加速電圧が１００〜２５０ｋＶであることが好ましく、１２０〜１９０ｋＶであることがより好ましく、１５０〜１９０ｋＶであることが更に好ましい。また、照射線量は５〜４５ｋＧｙであることが好ましく、１０〜４０ｋＧｙであることがより好ましい。加速電圧が上記範囲内であれば、電子線を樹脂シート前駆体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、得られる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。 The electron beam irradiation may be carried out by subjecting the resin sheet precursor to a crosslinking treatment, for example, by irradiating an electron beam from one side or both sides of the film-formed resin sheet precursor. The conditions for electron beam irradiation depend on the thickness of the resin sheet precursor, but the acceleration voltage is preferably 100 to 250 kV, more preferably 120 to 190 kV, and further preferably 150 to 190 kV. .. The irradiation dose is preferably 5 to 45 kGy, more preferably 10 to 40 kGy. When the accelerating voltage is within the above range, the electron beam can sufficiently reach deep in the thickness direction of the resin sheet precursor, and the deterioration of the backing paper by the electron beam can be suppressed. Further, when the irradiation dose is within the above range, it becomes easy to perform desired cross-linking on the resin sheet while suppressing yellowing of the obtained resin sheet and changes in mechanical properties.
上記で得られた樹脂シートは、所望により電子線照射以外の架橋処理が更に施されていてもよい。この場合の架橋処理としては、過熱蒸気処理、水架橋処理を行うことができる。この場合、シラン架橋性樹脂の一部又は全部が架橋される。 The resin sheet obtained above may be optionally subjected to a crosslinking treatment other than electron beam irradiation. As the crosslinking treatment in this case, superheated steam treatment or water crosslinking treatment can be performed. In this case, a part or all of the silane crosslinkable resin is crosslinked.
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樹脂シートを配し、樹脂シート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 of performing superheated steam (also referred to as superheated steam) for 20 seconds to 15 minutes in an environment of 130°C to 280°C. Examples of the superheated steam treatment include a method in which a resin sheet is arranged in a superheated steam atmosphere and the superheated steam is brought into contact with the resin sheet. Moreover, as a method of water-crosslinking, the method of carrying out water-crosslinking by curing for 1 day to 1 month in a temperature range of 40° C. to 70° C. in an environment having a humidity of 60% or more, specifically, 40° C. Examples include a method of curing and water-crosslinking in an environment of a 90% constant temperature and humidity chamber.
電子線照射以外の架橋処理は、樹脂組成物を製膜したものに施してもよく、電子線照射により積層シートとした後に施してもよい。なお、過熱蒸気処理を行う架橋処理は、樹脂シート前駆体を基材上にラミネートして得られた積層シート前駆体、又は積層シートに施すことが好ましい。 The cross-linking treatment other than electron beam irradiation may be applied to the resin composition formed into a film, or may be applied after forming a laminated sheet by electron beam irradiation. In addition, it is preferable that the cross-linking treatment in which the superheated steam treatment is performed is performed on the laminated sheet precursor obtained by laminating the resin sheet precursor on the substrate, or the laminated sheet.
［発泡壁紙の製造方法］
本実施形態に係る発泡壁紙は、基材と、該基材上に設けられた発泡樹脂層と、を備える。発泡壁紙の製造方法は、上述した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発泡樹脂層を形成する工程を備える。積層シートは上述した積層シートの製造方法により得ることができる。
[Method for producing foamed wallpaper]
The foamed wallpaper according to the present embodiment includes a base material and a foamed resin layer provided on the base material. The method for producing a foamed wallpaper includes a step of forming a foamed resin layer by foaming a foaming agent contained in the resin sheet in the laminated sheet described above. The laminated sheet can be obtained by the method for producing a laminated sheet described above.
発泡剤の発泡は、上記積層シートにおける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。 The foaming of the foaming agent can be performed by heating the resin sheet in the laminated sheet. The heating conditions can be appropriately set depending on the components constituting the resin sheet and are not particularly limited, but heating at 160° C. to 280° C. for 10 seconds to 120 seconds is preferable, and 220° C. to 240° C. is 20. It is more preferable to heat for 2 seconds to 40 seconds, and it is further preferable to heat at 220°C for 40 seconds.
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る。これらは、目的に応じて適宜選択可能であり、複数を組み合わせてもよい。 Further, 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, but, for example, by utilizing the heat at the time of heat foaming, the surface side is the cooling embossing roll, the substrate side is the rubber roll, and two tolls are used. Examples include a method of forming an uneven shape on the surface by nipping (embossing) and cooling. The uneven shape is not particularly limited, but examples thereof include wood grain board conduit groove, stone board surface unevenness, cloth surface texturer, satin finish, grain, hairline, and line groove. These can be appropriately selected according to the purpose, and a plurality of them may be combined.
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 this embodiment may be provided with a pattern layer and a surface protection layer. The pattern layer and the surface protective layer can be appropriately provided by 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 by using a known printing technique such as gravure coating. The pattern layer and the surface protective layer can be provided before foaming the foaming agent.
以下、実施例、参考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 , Reference 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、参考例２〜３、実施例４、参考例５〜６、比較例１〜３）
円形のインフレーションダイを取り付けた単軸押出機を用い、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１３０℃、厚み１００μｍで製膜し、樹脂シート前駆体をそれぞれ得た。
[Preparation of foam wallpaper]
(Example 1 , Reference Examples 2-3, Example 4, Reference Examples 5-6 , Comparative Examples 1-3)
Using a single-screw extruder equipped with a circular inflation die, a resin composition having the composition shown in Table 1 (numerical values in the table indicate parts by mass) is formed at an extrusion temperature of 130° C. and a thickness of 100 μm, Resin sheet precursors were obtained respectively.
次に、裏打紙（ＫＪ特殊紙製、ＷＫ−６６５１ＨＴ、重量６５ｇ／ｍ２）上に、実施例、参考例及び比較例で製膜した樹脂シート前駆体を置き、１１０℃で加熱した熱プレス機で３０秒間プレスして熱融着させ、積層シート前駆体を得た。その後、実施例１、参考例２〜３、実施例４、参考例５〜６及び比較例２の積層シート前駆体に対しては、上記樹脂シート前駆体側から加速電圧２００ｋＶ、電子線量２０ｋＧｙの条件で電子線を照射して樹脂シート前駆体を樹脂シートとし、裏打紙上に樹脂シートが設けられた積層シートを得た。その後、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。なお、比較例３の積層シート前駆体に対しては、上記樹脂シート前駆体側から加速電圧２００ｋＶ、電子線量５０ｋＧｙの条件で電子線を照射して樹脂シート前駆体を樹脂シートとし、裏打紙上に樹脂シートが設けられた積層シートを得た。その後、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。また、比較例１の積層シート前駆体に対しては、上述した電子線の照射を行わずに、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。 Next, the backing paper (made by KJ special paper, WK-6651HT, weight 65 g/m 2 ) was placed on the resin sheet precursors formed in Examples , Reference Examples and Comparative Examples, and heated at 110° C. A laminated sheet precursor was obtained by pressing for 30 seconds with a machine and heat fusion. After that, for the laminated sheet precursors of Example 1 , Reference Examples 2 to 3, Example 4, Reference Examples 5 to 6 and Comparative Example 2, conditions of an acceleration voltage of 200 kV and an electron dose of 20 kGy from the resin sheet precursor side. Then, the resin sheet precursor was made into a resin sheet by irradiating with an electron beam to obtain a laminated sheet in which the resin sheet was provided on the backing paper. After that, it was heated in an oven at 240° C. for 25 seconds to foam the foaming agent to prepare a foamed wallpaper. The laminated sheet precursor of Comparative Example 3 was irradiated with an electron beam from the resin sheet precursor side under the conditions of an accelerating voltage of 200 kV and an electron dose of 50 kGy to form a resin sheet precursor into a resin sheet, and a resin was placed on the backing paper. A laminated sheet provided with the sheet was obtained. Then, it heated in a 240 degreeC oven for 25 seconds, the foaming agent was foamed, and the foaming wallpaper was produced. Further, the laminated sheet precursor of Comparative Example 1 was heated in an oven at 240° C. for 25 seconds without being irradiated with the above-mentioned electron beam to foam the foaming agent to prepare a foamed wallpaper.
［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、表面状態、セルサイズ、及び圧縮回復性を評価した。また、下記に示すコーンカロリー難燃性試験により、作製した発泡壁紙の総発熱量、最大発熱速度、及び２００ｋＷ超過時間を評価した。各評価結果を表１に示す。
[Evaluation of foam wallpaper]
The foamed wallpaper thus produced was evaluated for foaming ratio, surface condition, cell size, and compression recovery according to the following methods. Moreover, the total calorific value, the maximum heat generation rate, and the 200 kW excess time of the produced foamed wallpaper were evaluated by the corn calorie flame retardancy test shown below. The results of each evaluation are shown in Table 1.
（発泡倍率）
厚み計を用いて発泡壁紙の裏打紙込みの厚みＴ（μｍ）を測定した。この値から下記式により発泡倍率を算出した。
発泡倍率＝［Ｔ−（裏打紙の厚み）］／（樹脂シートの厚み）
［なお、裏打紙の厚み及び樹脂シートの厚みはそれぞれ１００μｍ］
(Expansion ratio)
The thickness T (μm) of the backing paper of the foamed wallpaper was measured using a thickness meter. From this value, the expansion ratio was calculated by the following formula.
Foaming ratio=[T-(thickness of backing paper)]/(thickness of resin sheet)
[Note that the thickness of the backing paper and the thickness of the resin sheet are each 100 μm]
（表面状態）
目視にて、表層からのガス抜けの有無を確認し、下記の判定基準に従い評価した。
Ａ：表層に孔が見られない。
Ｂ：表層にクレーター状の孔が確認された（ガス抜け有り）。
(Surface condition)
The presence or absence of gas escape from the surface layer was visually confirmed and evaluated according to the following criteria.
A: No holes are seen in the surface layer.
B: Crater-like pores were confirmed on the surface layer (out of gas).
（セルサイズ）
作製した発泡壁紙を断面カットし、×１００の光学顕微鏡（キーエンス製マイクロスコープ、ＶＨＸ６００）を使用してセルサイズを目視確認した。視野内の最大セルに着目し、その最大サイズ（幅方向）を測定した。
(Cell size)
The produced foamed wallpaper was cut in cross section, and the cell size was visually confirmed using a ×100 optical microscope (Keyence microscope, VHX600). Focusing on the largest cell in the visual field, the maximum size (width direction) was measured.
（圧縮回復性）
作製した発泡壁紙を２ｃｍ×２ｃｍの大きさの試験片に裁断し、圧縮前の試験片の厚み（ｃ）を測定し、これを初期値とした。次に、２枚の金属製の平板で試験片を挟み、１００ｋｇｆ／ｃｍ２の圧力をかけて４０℃環境下で１日間放置した。その後、圧力を開放し、試験片の厚み（ｄ）を測定し、（ｄ）×１００／（ｃ）を圧縮回復率として算出した。
(Compression recovery)
The produced foamed wallpaper was cut into a test piece having a size of 2 cm×2 cm, and the thickness (c) of the test piece before compression was measured and used as the initial value. Next, the test piece was sandwiched between two metal flat plates, and a pressure of 100 kgf/cm 2 was applied, and the test piece was allowed to stand for 1 day in an environment of 40°C. Then, the pressure was released, the thickness (d) of the test piece was measured, and (d)×100/(c) was calculated as the compression recovery rate.
［コーンカロリー難燃性試験］
ＩＳＯ５６６０−１に定められた測定方法に基づき、酸素消費法と呼ばれる原理を用いて発熱速度及び発熱量を求めた。より具体的には、１０ｃｍ×１０ｃｍにカットした評価用シートの裏面に５ｇの接着剤（ルーアマイルド ヤヨイ化学製）を塗布し、同じく１０ｃｍ×１０ｃｍにカットした石膏ボード上に、接着剤面を介して貼り合わせ、室温環境下で１週間養生させてサンプルを作製した。試験装置は、株式会社東洋精機製作所製のコーンカロリーメーターＣ４型を用いて行った。酸素消費量をモニタリングし、発熱速度及び発熱量に換算した。なお、これは、燃焼によって発生する熱量は、燃焼する物質の重量あたりで考えると物質ごとに異なるが、消費される酸素の重量で考えると、物質の種類によらずほぼ一定の数値（酸素１ｋｇあたり１３．１×１０３ｋＪ）になるという原理に基づく。
[Corn calorie flame retardancy test]
Based on the measuring method defined in ISO5660-1, the heat generation rate and the heat generation amount were obtained using the principle called the oxygen consumption method. More specifically, 5 g of adhesive (manufactured by Rua Mild Yayoi Chemical Co., Ltd.) was applied to the back surface of the evaluation sheet cut into 10 cm×10 cm, and the adhesive surface was placed on the gypsum board similarly cut into 10 cm×10 cm. And pasted together and allowed to cure for 1 week in a room temperature environment to prepare a sample. A corn calorimeter C4 type manufactured by Toyo Seiki Seisakusho Co., Ltd. was used as a test device. Oxygen consumption was monitored and converted into heat generation rate and heat generation amount. It should be noted that the amount of heat generated by combustion differs from substance to substance when it is considered on the basis of the weight of the substance to be burned, but when considering the weight of oxygen consumed, it is almost constant regardless of the type of substance (oxygen 1 kg It is based on the principle that it becomes 13.1×10 3 kJ).
（裏打紙の黄変の有無）
電子線照射を行う前の裏打紙と、照射後の裏打紙とを比較して、その差が目視で容易に分かる場合を「黄変有り」、そうでない場合を「黄変無し」とした。
(Presence or absence of yellowing on the backing paper)
The backing paper before the electron beam irradiation was compared with the backing paper after the irradiation, and when the difference was easily visually recognizable, "yellowing was present", and when not so, "no yellowing".
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−１：ノバテックＬＤ ＬＪ８０２Ａ（日本ポリエチレン製、商品名、ＭＦＲ＝２７、密度＝０．９１７）
樹脂Ａ−２：ノバテックＬＤ ＬＣ６００Ａ（日本ポリエチレン製、商品名、ＭＦＲ＝７、密度＝０．９１８）
樹脂Ａ−３：ペトロセン３５３（東ソー製、商品名、ＭＦＲ＝１４５、密度０．９１５）
[Low density polyethylene]
Resin A-1: Novatec LD LJ802A (manufactured by Japan Polyethylene, trade name, MFR=27, density=0.917)
Resin A-2: Novatec LD LC600A (manufactured by Japan Polyethylene, trade name, MFR=7, density=0.918)
Resin A-3: Petrosene 353 (manufactured by Tosoh Corporation, trade name, MFR=145, density 0.915)
［超低密度ポリエチレン］
樹脂Ｂ−１：タフマー ＤＦ７３５０（三井化学製、商品名、ＭＦＲ＝３５、密度０．８７０）
[Ultra low density polyethylene]
Resin B-1: Tufmer DF7350 (manufactured by Mitsui Chemicals, trade name, MFR=35, density 0.870)
［その他の樹脂］
シラン架橋性樹脂：リンクロン ＸＣＦ７１０Ｎ（三菱化学製、商品名、低密度ポリエチレンベース）
[Other resins]
Silane cross-linkable resin: LINKRON XCF710N (Mitsubishi Chemical, trade name, low density polyethylene base)
［充填剤］
炭酸カルシウム：ＢＦ２００Ｓ（備北粉化工業製、商品名、５０％平均粒径５μｍ）
二酸化チタン：タイペークＣＲ−６０（石原産業製、商品名、５０％平均粒径０．２１μｍ）
[filler]
Calcium carbonate: BF200S (manufactured by Bihoku Powder Co., Ltd., trade name, 50% average particle size 5 μm)
Titanium dioxide: TAIPAKE CR-60 (manufactured by Ishihara Sangyo, trade name, 50% average particle size 0.21 μm)
［発泡剤］
アゾ系発泡剤：ビニホールＡＣ＃３Ｃ−Ｋ２（永和化成工業製、商品名、平均粒径５μｍ）
ヒドラジド系発泡剤：ネオセルボンＮ＃１０００Ｍ（永和化成工業製、商品名、平均粒径４μｍ）
[Foaming agent]
Azo-based foaming agent: Vinylhol AC#3C-K2 (manufactured by Eiwa Chemical Industry Co., Ltd., trade name, average particle size 5 μm)
Hydrazide-based blowing agent: Neocerbon N#1000M (manufactured by Eiwa Chemical Industry, trade name, average particle size 4 μm)
［発泡助剤］
亜鉛系発泡助剤：アデカスタブＯＦ１０１（ＡＤＥＫＡ製、商品名、粉状品）
[Foaming aid]
Zinc-based foaming aid: ADEKA STAB OF101 (made by ADEKA, trade name, powder product)
［水和金属化合物］
水酸化アルミニウムＡ：Ｂ−３０３（巴工業製、商品名、平均粒径４．３μｍ）
水酸化アルミニウムＢ：Ｂ−３０９（巴工業製、商品名、平均粒径１１．５μｍ）
水酸化マグネシウム：キスマ８（協和化学工業製、商品名、平均粒径１．６７μｍ）
[Hydrated metal compound]
Aluminum hydroxide A: B-303 (trade name, average particle size 4.3 μm, manufactured by Tomoe Kogyo)
Aluminum hydroxide B: B-309 (manufactured by Tomoe Kogyo, trade name, average particle size 11.5 μm)
Magnesium hydroxide: Kisuma 8 (Kyowa Chemical Industry, trade name, average particle size 1.67 μm)
［その他の添加剤］
シラン架橋助剤：ＬＺ０１３（三菱化学製、商品名、ポリエチレンベース）
[Other additives]
Silane crosslinking aid: LZ013 (Mitsubishi Chemical, trade name, polyethylene base)
表１から分かるように、水和金属化合物を添加した樹脂組成物から形成された樹脂シート前駆体に対し、電子線照射を施すことで、裏打紙の黄変が発生しにくい照射条件であっても、十分な発泡倍率を有し、かつ発泡後の表面状態が良好な発泡壁紙を得ることができる。さらに、水和金属化合物の難燃効果により最大発熱速度及び２００ｋＷ超過時間の数値を抑制することができる。このことは、特に水酸化アルミニウムを添加した場合に顕著である。また、平均粒径の小さい水和金属化合物を用いることで、表面積を増やした場合に更に顕著である。
As can be seen from Table 1, the resin sheet precursor formed from the resin composition to which the hydrated metal compound was added was subjected to electron beam irradiation, so that the yellowing of the backing paper was less likely to occur. Also, a foamed wallpaper having a sufficient expansion ratio and having a good surface condition after foaming can be obtained. Further, the flame retardant effect of the hydrated metal compound makes it possible to suppress the maximum heat generation rate and the numerical value of the 200 kW excess time. This is remarkable especially when aluminum hydroxide is added. Further, it is more remarkable when the surface area is increased by using a hydrated metal compound having a small average particle size.
Claims (4)
メルトフローレートが１０〜１００である低密度ポリエチレンと、発泡剤と、シラン架橋性ポリオレフィン系樹脂と、平均粒径が５μｍ以下である水酸化アルミニウムと、を含む樹脂組成物を製膜して得られる樹脂シート前駆体を基材上にラミネートして積層シート前駆体を得る工程と、
前記積層シート前駆体における前記樹脂シート前駆体を電子線の照射により樹脂シートとし、前記基材上に前記樹脂シートが設けられた積層シートを得る工程と、
前記積層シートにおける前記樹脂シートに含まれる前記発泡剤を発泡させて発泡樹脂層を形成する工程と、
を備え、
前記シラン架橋性ポリオレフィン系樹脂の含有量が、前記樹脂組成物全量を基準として、３〜１０質量％である、発泡壁紙の製造方法。 A method for producing a foamed wallpaper comprising a base material and a foamed resin layer provided on the base material,
Obtained by forming a resin composition containing low density polyethylene having a melt flow rate of 10 to 100, a foaming agent, a silane crosslinkable polyolefin resin, and aluminum hydroxide having an average particle size of 5 μm or less. A step of laminating a resin sheet precursor to be obtained on a substrate to obtain a laminated sheet precursor;
A step of obtaining a laminated sheet in which the resin sheet is provided on the base material by irradiating the resin sheet precursor with a resin sheet in the laminated sheet precursor with an electron beam;
Forming a foamed resin layer by foaming the foaming agent contained in the resin sheet in the laminated sheet;
Equipped with
The method for producing a foamed wallpaper, wherein the content of the silane crosslinkable polyolefin-based resin is 3 to 10% by mass based on the total amount of the resin composition.
メルトフローレートが１０〜１００である低密度ポリエチレンと、発泡剤と、シラン架橋性ポリオレフィン系樹脂と、平均粒径が５μｍ以下である水酸化アルミニウムと、を含む樹脂組成物を製膜して得られる樹脂シート前駆体を基材上にラミネートして積層シート前駆体を得る工程と、
前記積層シート前駆体における前記樹脂シート前駆体を電子線の照射により樹脂シートとし、前記基材上に前記樹脂シートが設けられた積層シートを得る工程と、
を備え、
前記シラン架橋性ポリオレフィン系樹脂の含有量が、前記樹脂組成物全量を基準として、３〜１０質量％である、積層シートの製造方法。 A method for producing a laminated sheet, comprising a base material and a resin sheet provided on the base material,
Obtained by forming a resin composition containing low density polyethylene having a melt flow rate of 10 to 100, a foaming agent, a silane crosslinkable polyolefin resin, and aluminum hydroxide having an average particle size of 5 μm or less. A step of laminating a resin sheet precursor to be obtained on a substrate to obtain a laminated sheet precursor;
A step of obtaining a laminated sheet in which the resin sheet is provided on the base material by irradiating the resin sheet precursor with a resin sheet in the laminated sheet precursor with an electron beam;
Equipped with
The method for producing a laminated sheet, wherein the content of the silane crosslinkable polyolefin-based resin is 3 to 10% by mass based on the total amount of the resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015012101A JP6733130B2 (en) | 2015-01-26 | 2015-01-26 | Method for producing foamed wallpaper and method for producing laminated sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015012101A JP6733130B2 (en) | 2015-01-26 | 2015-01-26 | Method for producing foamed wallpaper and method for producing laminated sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016138361A JP2016138361A (en) | 2016-08-04 |
| JP6733130B2 true JP6733130B2 (en) | 2020-07-29 |
Family
ID=56558318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015012101A Active JP6733130B2 (en) | 2015-01-26 | 2015-01-26 | Method for producing foamed wallpaper and method for producing laminated sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6733130B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6870277B2 (en) * | 2016-10-28 | 2021-05-12 | 凸版印刷株式会社 | Laminated sheet, foam wallpaper, and method of manufacturing foam wallpaper |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60179427A (en) * | 1984-02-24 | 1985-09-13 | Toray Ind Inc | Polyolefin foam |
| JPS61228034A (en) * | 1985-04-02 | 1986-10-11 | Mitsubishi Petrochem Co Ltd | Foaming agent master batch resin composition |
| JPH0710934B2 (en) * | 1990-06-25 | 1995-02-08 | 積水化学工業株式会社 | Method for producing flame-retardant resin crosslinked foam |
| JP3520909B2 (en) * | 1999-09-30 | 2004-04-19 | 積水化成品工業株式会社 | Polyolefin resin foam and method for producing the same |
| JP2002113733A (en) * | 2000-10-06 | 2002-04-16 | Sekisui Chem Co Ltd | Polyolefinic resin foam |
| JP4160874B2 (en) * | 2002-08-06 | 2008-10-08 | 三井化学株式会社 | Wallpaper and manufacturing method thereof |
| KR100767014B1 (en) * | 2005-10-17 | 2007-10-15 | 전효철 | Aqueous foam wallpaper for improving embossable plasticity and Method for manufacturing thereof |
| JP5412542B2 (en) * | 2012-03-21 | 2014-02-12 | 日東電工株式会社 | Foamable sealing material, foamable sealing member, sealing foam, and space sealing method |
| JP2014173217A (en) * | 2013-03-13 | 2014-09-22 | Toppan Cosmo Inc | Foamed wallpaper and method for manufacturing the same |
-
2015
- 2015-01-26 JP JP2015012101A patent/JP6733130B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016138361A (en) | 2016-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6733130B2 (en) | Method for producing foamed wallpaper and method for producing laminated sheet | |
| JP6720631B2 (en) | Resin composition, method for producing resin sheet, method for producing laminated sheet, and method for producing foamed wallpaper | |
| JP6520138B2 (en) | Resin composition, resin sheet, laminated sheet and foam wallpaper | |
| JP6638277B2 (en) | Resin composition set, resin sheet, laminated sheet and foamed wallpaper, and method for producing resin sheet and foamed wallpaper | |
| JP6413696B2 (en) | Resin composition, resin sheet, laminated sheet and foamed wallpaper | |
| JP6485021B2 (en) | Resin composition, resin sheet, laminated sheet and foamed wallpaper | |
| JP6705248B2 (en) | Resin composition, method for producing resin sheet, method for producing laminated sheet, and method for producing foamed wallpaper | |
| JP6554961B2 (en) | Resin sheet, laminated sheet and foam wallpaper | |
| JP6728872B2 (en) | Resin composition, method for producing resin sheet, method for producing laminated sheet, and method for producing foamed wallpaper | |
| JP2017088802A (en) | Resin composition, manufacturing method of resin sheet, manufacturing method of laminate sheet and manufacturing method of foam wallpaper | |
| JP6582504B2 (en) | RESIN COMPOSITION, LAMINATED SHEET, LAMINATE, FOAM WALLPAPER AND METHOD FOR PRODUCING FOAM WALLPAPER | |
| JP6569299B2 (en) | Resin composition, resin sheet, laminated sheet and foamed wallpaper | |
| JP6554797B2 (en) | RESIN COMPOSITION, LAMINATED SHEET, LAMINATE, FOAM WALLPAPER AND METHOD FOR PRODUCING FOAM WALLPAPER | |
| JP6705235B2 (en) | Resin composition, method for producing resin sheet, method for producing laminated sheet, and method for producing foamed wallpaper | |
| JP6536172B2 (en) | Resin composition, resin sheet, laminated sheet and foam wallpaper | |
| JP6690274B2 (en) | Method for manufacturing laminated sheet and foam wallpaper | |
| JP2017088746A (en) | Resin composition, and manufacturing method of resin sheet, laminate sheet and foam wallpaper | |
| JP6645010B2 (en) | Resin composition, resin sheet, laminated sheet and foamed wallpaper | |
| JP6413557B2 (en) | Resin composition, resin sheet, laminated sheet and foamed wallpaper | |
| JP6511932B2 (en) | Resin composition, resin sheet, laminated sheet and foam wallpaper | |
| JP6492494B2 (en) | Resin composition, resin sheet, laminated sheet and foamed wallpaper | |
| JP6384224B2 (en) | RESIN COMPOSITION, LAMINATED SHEET, LAMINATE, FOAM WALLPAPER AND METHOD FOR PRODUCING FOAM WALLPAPER | |
| JP2017100398A (en) | Multilayer resin sheet, laminated sheet, method for producing multilayer resin sheet, method for producing laminated sheet, and method for producing foamed wall paper | |
| JP6492482B2 (en) | Resin composition, resin sheet, laminated sheet and foamed wallpaper | |
| JP6520434B2 (en) | Resin composition, resin sheet, laminated sheet and foam wallpaper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20160603 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20160617 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20171220 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20181009 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181106 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181211 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190521 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190614 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20191203 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200121 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200609 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200622 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6733130 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |