JP2023177156A - Flame-retardant composition, and flame-retardant synthetic leather using the same - Google Patents
Flame-retardant composition, and flame-retardant synthetic leather using the same Download PDFInfo
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- JP2023177156A JP2023177156A JP2022089928A JP2022089928A JP2023177156A JP 2023177156 A JP2023177156 A JP 2023177156A JP 2022089928 A JP2022089928 A JP 2022089928A JP 2022089928 A JP2022089928 A JP 2022089928A JP 2023177156 A JP2023177156 A JP 2023177156A
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- Prior art keywords
- flame
- retardant
- synthetic leather
- resin
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 160
- 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 title claims abstract description 155
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 239000002649 leather substitute Substances 0.000 title claims abstract description 70
- 229920005989 resin Polymers 0.000 claims abstract description 60
- 239000011347 resin Substances 0.000 claims abstract description 60
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 54
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 31
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 31
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 150000002829 nitrogen Chemical class 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 105
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 67
- 239000012790 adhesive layer Substances 0.000 claims description 60
- 229920005749 polyurethane resin Polymers 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000007788 liquid Substances 0.000 abstract description 32
- 238000012545 processing Methods 0.000 abstract description 22
- 230000007774 longterm Effects 0.000 abstract description 13
- 230000007547 defect Effects 0.000 abstract description 9
- 230000008719 thickening Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 210000003491 skin Anatomy 0.000 description 45
- -1 black Substances 0.000 description 39
- 239000003431 cross linking reagent Substances 0.000 description 27
- 239000002245 particle Substances 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 25
- 238000001035 drying Methods 0.000 description 17
- 229920002635 polyurethane Polymers 0.000 description 17
- 239000004814 polyurethane Substances 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000002335 surface treatment layer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920000515 polycarbonate Polymers 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011135 tin Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 239000003086 colorant Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 239000010985 leather Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 210000002615 epidermis Anatomy 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- WVLAZEHCUADXTN-UHFFFAOYSA-K aluminum butyl(ethyl)phosphinate Chemical compound [Al+3].CCCCP([O-])(=O)CC.CCCCP([O-])(=O)CC.CCCCP([O-])(=O)CC WVLAZEHCUADXTN-UHFFFAOYSA-K 0.000 description 3
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 3
- 150000001463 antimony compounds Chemical class 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- DZOOETXSZAIPSN-UHFFFAOYSA-J CP([O-])(=O)CCC.[Ti+4].CP([O-])(=O)CCC.CP([O-])(=O)CCC.CP([O-])(=O)CCC Chemical compound CP([O-])(=O)CCC.[Ti+4].CP([O-])(=O)CCC.CP([O-])(=O)CCC.CP([O-])(=O)CCC DZOOETXSZAIPSN-UHFFFAOYSA-J 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QVKQNISQFCPYGN-UHFFFAOYSA-K aluminum;dimethylphosphinate Chemical compound [Al+3].CP(C)([O-])=O.CP(C)([O-])=O.CP(C)([O-])=O QVKQNISQFCPYGN-UHFFFAOYSA-K 0.000 description 2
- XDMYAHBAPIRGTQ-UHFFFAOYSA-K aluminum;methyl(propyl)phosphinate Chemical compound [Al+3].CCCP(C)([O-])=O.CCCP(C)([O-])=O.CCCP(C)([O-])=O XDMYAHBAPIRGTQ-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- DRYHXHUXMMIMPH-UHFFFAOYSA-L calcium;diethylphosphinate Chemical compound [Ca+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DRYHXHUXMMIMPH-UHFFFAOYSA-L 0.000 description 2
- DONULGYRZAGJQH-UHFFFAOYSA-L calcium;dimethylphosphinate Chemical compound [Ca+2].CP(C)([O-])=O.CP(C)([O-])=O DONULGYRZAGJQH-UHFFFAOYSA-L 0.000 description 2
- BFKPORWCVZVLTQ-UHFFFAOYSA-L calcium;ethyl(methyl)phosphinate Chemical compound [Ca+2].CCP(C)([O-])=O.CCP(C)([O-])=O BFKPORWCVZVLTQ-UHFFFAOYSA-L 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- HFVKYLPSHXAMME-UHFFFAOYSA-J diethylphosphinate;titanium(4+) Chemical compound [Ti+4].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC HFVKYLPSHXAMME-UHFFFAOYSA-J 0.000 description 2
- 150000002013 dioxins Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- OKGBOBQVOXYHQP-UHFFFAOYSA-J ethyl(methyl)phosphinate titanium(4+) Chemical compound [Ti+4].CCP(C)([O-])=O.CCP(C)([O-])=O.CCP(C)([O-])=O.CCP(C)([O-])=O OKGBOBQVOXYHQP-UHFFFAOYSA-J 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
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- 238000002604 ultrasonography Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- MXMCTPBQIJWVBA-UHFFFAOYSA-L zinc;dimethylphosphinate Chemical compound [Zn+2].CP(C)([O-])=O.CP(C)([O-])=O MXMCTPBQIJWVBA-UHFFFAOYSA-L 0.000 description 2
- GYKKGOMJFMCRIN-UHFFFAOYSA-L zinc;ethyl(methyl)phosphinate Chemical compound [Zn+2].CCP(C)([O-])=O.CCP(C)([O-])=O GYKKGOMJFMCRIN-UHFFFAOYSA-L 0.000 description 2
- GLDFMLDAWXHNQU-UHFFFAOYSA-L zinc;methyl(propyl)phosphinate Chemical compound [Zn+2].CCCP(C)([O-])=O.CCCP(C)([O-])=O GLDFMLDAWXHNQU-UHFFFAOYSA-L 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- GHCFWKFREBNSPC-UHFFFAOYSA-N 2-Amino-4-methylpyrimidine Chemical compound CC1=CC=NC(N)=N1 GHCFWKFREBNSPC-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
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- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
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- 208000027418 Wounds and injury Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
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- 239000012964 benzotriazole Substances 0.000 description 1
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- SPWAXFLJYHRRJL-UHFFFAOYSA-N butyl(ethyl)phosphinic acid Chemical compound CCCCP(O)(=O)CC SPWAXFLJYHRRJL-UHFFFAOYSA-N 0.000 description 1
- MHDPBLKGZFXUOG-UHFFFAOYSA-N butyl(hexyl)phosphinic acid Chemical compound CCCCCCP(O)(=O)CCCC MHDPBLKGZFXUOG-UHFFFAOYSA-N 0.000 description 1
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- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 1
- LITFOGPYONJRNO-UHFFFAOYSA-L calcium phosphinate Chemical compound [Ca+2].[O-]P=O.[O-]P=O LITFOGPYONJRNO-UHFFFAOYSA-L 0.000 description 1
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- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 1
- NGKCHGKFHQDOPZ-UHFFFAOYSA-N dihexylphosphinic acid Chemical compound CCCCCCP(O)(=O)CCCCCC NGKCHGKFHQDOPZ-UHFFFAOYSA-N 0.000 description 1
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- 238000009837 dry grinding Methods 0.000 description 1
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- 239000000839 emulsion Substances 0.000 description 1
- WLPKFQRBARNCNR-UHFFFAOYSA-N ethene 1,3,5-triazine-2,4,6-triamine Chemical compound C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 WLPKFQRBARNCNR-UHFFFAOYSA-N 0.000 description 1
- AGWPTXYSXUNKLV-UHFFFAOYSA-N ethoxy-methyl-oxophosphanium Chemical compound CCO[P+](C)=O AGWPTXYSXUNKLV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- RMMXRAVNFLSFDE-UHFFFAOYSA-N ethyl(hexyl)phosphinic acid Chemical compound CCCCCCP(O)(=O)CC RMMXRAVNFLSFDE-UHFFFAOYSA-N 0.000 description 1
- BXDCELKJGGVUHD-UHFFFAOYSA-N ethyl(methyl)phosphane Chemical compound CCPC BXDCELKJGGVUHD-UHFFFAOYSA-N 0.000 description 1
- NXHKQBCTZHECQF-UHFFFAOYSA-N ethyl(methyl)phosphinic acid Chemical compound CCP(C)(O)=O NXHKQBCTZHECQF-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- YMAWOPBAYDPSLA-UHFFFAOYSA-N glycine anhydride Natural products [NH3+]CC(=O)NCC([O-])=O YMAWOPBAYDPSLA-UHFFFAOYSA-N 0.000 description 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011254 layer-forming composition Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SZTJCIYEOQYVED-UHFFFAOYSA-N methyl(propyl)phosphinic acid Chemical compound CCCP(C)(O)=O SZTJCIYEOQYVED-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BXRNXXXXHLBUKK-UHFFFAOYSA-N piperazine-2,5-dione Chemical compound O=C1CNC(=O)CN1 BXRNXXXXHLBUKK-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- SLKRGHBFYYVSLH-UHFFFAOYSA-K tris(dibutylphosphoryloxy)alumane Chemical compound [Al+3].CCCCP([O-])(=O)CCCC.CCCCP([O-])(=O)CCCC.CCCCP([O-])(=O)CCCC SLKRGHBFYYVSLH-UHFFFAOYSA-K 0.000 description 1
- ILMYTDDXICIZAE-UHFFFAOYSA-K tris(dihexylphosphoryloxy)alumane Chemical compound CCCCCCP(=O)(CCCCCC)O[Al](OP(=O)(CCCCCC)CCCCCC)OP(=O)(CCCCCC)CCCCCC ILMYTDDXICIZAE-UHFFFAOYSA-K 0.000 description 1
- KKRWIYARCZDAEV-UHFFFAOYSA-K tris[[butyl(hexyl)phosphoryl]oxy]alumane Chemical compound CCCCCCP(=O)(CCCC)O[Al](OP(=O)(CCCC)CCCCCC)OP(=O)(CCCC)CCCCCC KKRWIYARCZDAEV-UHFFFAOYSA-K 0.000 description 1
- PLOCDMOCRZWIFH-UHFFFAOYSA-L zinc;butyl(ethyl)phosphinate Chemical compound [Zn+2].CCCCP([O-])(=O)CC.CCCCP([O-])(=O)CC PLOCDMOCRZWIFH-UHFFFAOYSA-L 0.000 description 1
- UMQIMEQYMIJDTR-UHFFFAOYSA-L zinc;dibutylphosphinate Chemical compound [Zn+2].CCCCP([O-])(=O)CCCC.CCCCP([O-])(=O)CCCC UMQIMEQYMIJDTR-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
- C09K21/04—Inorganic materials containing phosphorus
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Laminated Bodies (AREA)
- Fireproofing Substances (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は、難燃性組成物及びそれを用いた難燃性合成皮革に関する。 The present invention relates to a flame retardant composition and flame retardant synthetic leather using the same.
従来、合成皮革は、天然皮革の代替品として、あるいは、天然皮革以上に良好な物性を備えた皮革素材として、衣料、鞄、靴、インテリア資材、車両用内装材など様々な用途に用いられている。これらのうち、インテリア資材、車両用内装材は、火災時の人的被害を考慮し法的に厳しく規制されており、合成皮革にはこの規格をクリアする高い難燃性が求められている。 Conventionally, synthetic leather has been used for various purposes such as clothing, bags, shoes, interior materials, and vehicle interior materials, either as a substitute for natural leather or as a leather material with better physical properties than natural leather. There is. Among these, interior materials and vehicle interior materials are strictly regulated by law in consideration of human injury in the event of a fire, and synthetic leather is required to have high flame retardancy that meets these standards.
合成皮革は、天然皮革調の風合いを得るため、一般に、繊維質からなる基材（例えば、不織布、織物、編物など）に樹脂層（中間層、表皮層、表面処理層など）を積層して形成される。このような合成皮革を難燃化する方法としては、合成皮革を構成する各層（繊維質基材、樹脂層、さらに繊維質基材と樹脂層の間に接着層が設けられることもある）のうち少なくとも１つを難燃化する方法や、難燃層を新たに設ける方法などが報告されており、さらに、前者としては、繊維質基材に難燃剤を後加工により付与する方法や、繊維原料（ポリマー）に難燃剤を練り込む方法、繊維原料の重合時に難燃成分を共重合させる方法、樹脂層に難燃剤を練り込む方法、樹脂の重合時に難燃成分を共重合させる方法などが報告されている。 In order to obtain a natural leather-like texture, synthetic leather is generally made by laminating a resin layer (intermediate layer, skin layer, surface treatment layer, etc.) on a fibrous base material (e.g., nonwoven fabric, woven fabric, knitted fabric, etc.). It is formed. One way to make such synthetic leather flame retardant is to make each layer that makes up the synthetic leather (fibrous base material, resin layer, and sometimes an adhesive layer is provided between the fibrous base material and the resin layer). Methods to make at least one of these flame retardant and methods to newly provide a flame retardant layer have been reported. Methods include methods of kneading flame retardants into raw materials (polymer), methods of copolymerizing flame retardant components during polymerization of fiber raw materials, methods of kneading flame retardants into resin layers, methods of copolymerizing flame retardant components during polymerization of resin, etc. It has been reported.
樹脂層に難燃剤を練り込む方法では、樹脂と難燃剤を混合した難燃化樹脂液を作成し使用する。樹脂層の外観を調整する目的で顔料などの着色剤が含有される場合があるが、ブラックなどの定番色の場合は、製造効率を高めるため、樹脂液を多量に製造し、長期間かけて使用する。 In the method of kneading a flame retardant into the resin layer, a flame retardant resin liquid is prepared and used by mixing a resin and a flame retardant. Coloring agents such as pigments may be included to adjust the appearance of the resin layer, but in the case of standard colors such as black, resin liquid is manufactured in large quantities and over a long period of time to increase manufacturing efficiency. use.
難燃剤としては、従来、その優れた難燃性からハロゲン化合物が広く用いられてきた。また、難燃助剤としてアンチモン化合物を併用し、相乗的に難燃性を高めることが行われてきた。しかしながら、近年、環境問題に対する関心の高まりから、燃焼時にダイオキシン類をはじめ有毒なハロゲンガスを発生する虞のあるハロゲン化合物は、その使用が敬遠されている。また、アンチモン化合物も、人体に対する毒性が指摘されている。このため、非ハロゲン化合物、特にリン化合物による難燃化の検討が盛んである。 Conventionally, halogen compounds have been widely used as flame retardants due to their excellent flame retardancy. Furthermore, antimony compounds have been used together as flame retardant aids to synergistically enhance flame retardancy. However, in recent years, due to increasing interest in environmental issues, the use of halogen compounds, which may generate toxic halogen gases such as dioxins when burned, has been avoided. Furthermore, antimony compounds have also been pointed out to be toxic to the human body. For this reason, studies are actively being conducted on flame retardation using non-halogen compounds, especially phosphorus compounds.
例えば、特許文献１には、繊維質基材の一方の面に、リン系難燃剤としてジオルガニルホスフィン酸塩が添加されたホットメルトウレタンポリオールプレポリマーとウレタン硬化剤の反応により形成されるポリウレタン樹脂からなる表皮層、およびポリウレタン樹脂からなる保護層が順に積層されてなる難燃性合成皮革が開示されている。 For example, in Patent Document 1, a polyurethane formed by a reaction between a hot melt urethane polyol prepolymer to which diorganyl phosphinate is added as a phosphorus flame retardant and a urethane curing agent is coated on one side of a fibrous base material. A flame-retardant synthetic leather is disclosed in which a skin layer made of resin and a protective layer made of polyurethane resin are laminated in this order.
さらに、特許文献２には、繊維質基材の一方の面に湿気硬化型ポリウレタン樹脂からなる多孔質層、ポリウレタン樹脂からなる無孔質層が順に積層されてなる合成皮革であって、該多孔質層に難燃剤としてジオルガニルホスフィン酸塩を含有することを特徴とする難燃性合成皮革が開示されている。 Furthermore, Patent Document 2 discloses a synthetic leather in which a porous layer made of a moisture-curable polyurethane resin and a non-porous layer made of a polyurethane resin are laminated in this order on one side of a fibrous base material, Disclosed is a flame-retardant synthetic leather characterized by containing a diorganyl phosphinate as a flame retardant in the synthetic layer.
しかしながら、特許文献１及び２に記載のジオルガニルホスフィン酸塩を樹脂液に混合した場合、難燃剤凝集物の発生、樹脂液の経時での増粘により、加工不良（難燃性の低下等）が生じる問題があった。 However, when the diorganyl phosphinates described in Patent Documents 1 and 2 are mixed with a resin liquid, the formation of flame retardant aggregates and the increase in the viscosity of the resin liquid over time may result in poor processing (deterioration of flame retardancy, etc.). ).
本発明はこのような現状に鑑みてなされたものであり、使用時に難燃剤凝集物の発生や樹脂液の経時での増粘が少なく、長期的な加工安定性を実現し、加工不良が生じることがない難燃性組成物及びそれを用いた難燃性合成皮革を提供することを目的とする。 The present invention has been made in view of the current situation, and it reduces the generation of flame retardant aggregates during use and the increase in viscosity of the resin liquid over time, and achieves long-term processing stability, thereby preventing processing defects. The purpose of the present invention is to provide a flame-retardant composition and a flame-retardant synthetic leather using the same.
本発明者らは、上記目的を達成するために、検討を行った結果、所定のジアルキルホスフィン酸塩を含む難燃性組成物に硫酸カリウム及び／又は硫酸カルシウムをさらに添加することにより、樹脂液に混合した場合でも増粘が抑制されて長期間使用することができ、難燃剤凝集物の析出、さらには加工不良の発生を顕著に抑制又は防止することができることを見出し、本発明を完成させた。 In order to achieve the above object, the present inventors conducted studies and found that by further adding potassium sulfate and/or calcium sulfate to a flame retardant composition containing a predetermined dialkyl phosphinate, the resin liquid It was discovered that even when mixed with flame retardant, thickening is suppressed and it can be used for a long period of time, and the precipitation of flame retardant aggregates and the occurrence of processing defects can be significantly suppressed or prevented, and the present invention was completed. Ta.
上記目的を達成し得た本発明は下記のとおりである。
［１］（Ａ）下記一般式（１）で表されるジアルキルホスフィン酸塩と、（Ｂ）硫酸カリウム及び／又は硫酸カルシウムとを含有することを特徴とする、難燃性組成物。
［２］前記硫酸カリウム及び／又は硫酸カルシウムの含有量が１～１５０００ｐｐｍであることを特徴とする、上記［１］に記載の難燃性組成物。
［３］繊維質基材の一方の面上に、上記［１］又は［２］に記載の難燃性組成物及び樹脂を含む接着層と、表皮層とを順に含むことを特徴とする、難燃性合成皮革。
［４］前記樹脂がポリウレタン樹脂である、上記［３］に記載の難燃性合成皮革。
［５］前記樹脂１００質量部に対して、前記難燃性組成物を１～５０質量部含有することを特徴とする、上記［３］又は［４］に記載の難燃性合成皮革。
The present invention that achieves the above object is as follows.
[1] A flame-retardant composition containing (A) a dialkyl phosphinate represented by the following general formula (1) and (B) potassium sulfate and/or calcium sulfate.
[2] The flame-retardant composition according to [1] above, wherein the content of the potassium sulfate and/or calcium sulfate is 1 to 15,000 ppm.
[3] An adhesive layer containing the flame retardant composition and resin described in [1] or [2] above, and a skin layer are included in this order on one surface of the fibrous base material. Flame retardant synthetic leather.
[4] The flame-retardant synthetic leather according to [3] above, wherein the resin is a polyurethane resin.
[5] The flame-retardant synthetic leather according to [3] or [4] above, which contains 1 to 50 parts by mass of the flame-retardant composition based on 100 parts by mass of the resin.
本発明によれば、使用時に難燃剤凝集物の発生や樹脂液の経時での増粘が少なく、長期的な加工安定性を実現し、加工不良が生じることがない難燃性組成物及びそれを用いた難燃性合成皮革を提供することができる。 According to the present invention, there is provided a flame-retardant composition that does not generate agglomerates of flame retardant during use or increase the viscosity of resin liquid over time, achieves long-term processing stability, and does not cause processing defects. It is possible to provide flame-retardant synthetic leather using.
＜難燃性組成物＞
本発明の実施形態に係る難燃性組成物は、（Ａ）下記一般式（１）で表されるジアルキルホスフィン酸塩と、（Ｂ）硫酸カリウム及び／又は硫酸カルシウムとを含有することを特徴としている。
The flame retardant composition according to an embodiment of the present invention is characterized by containing (A) a dialkyl phosphinate represented by the following general formula (1), and (B) potassium sulfate and/or calcium sulfate. It is said that
例えば、合成皮革の難燃化を実現するため、繊維質基材と表皮層の間に設けられる接着層に難燃剤を配合する場合がある。この場合、難燃剤を配合した樹脂液（接着層形成用組成物）を乾燥させて接着層を形成するが、難燃剤としてジオルガニルホスフィン酸塩を配合した接着液を長時間使用していると、接着液が増粘して加工しづらくなり、さらには難燃剤凝集物の析出が生じることがある。その結果として、得られる難燃性合成皮革において接着層の接着効果が低下し、ひいては難燃性合成皮革の難燃性が低下するという問題があった。そこで、本発明者らは、このような問題に対処すべく、検討を行った結果、ジオルガニルホスフィン酸塩として所定のジアルキルホスフィン酸塩を含む難燃性組成物に硫酸カリウム及び／又は硫酸カルシウムをさらに添加することにより、当該難燃性組成物を樹脂液に混合した場合においても増粘が抑制されて長期間使用することができ、難燃剤凝集物の析出を顕著に抑制又は防止して長期的な加工安定性を実現するとともに、その結果として接着性の低下や難燃性の低下といった加工不良が生じることのない優れた難燃性合成皮革を提供することができることを見出した。したがって、本発明の実施形態に係る難燃性組成物によれば、意匠性や外観品位、風合いを損なうことなく高度な難燃性を有する合成皮革を、接着物性を損なうことなく長期的に製造することができる。また、このようにして製造された難燃性合成皮革は、例えば、ＦＭＶＳＳ（米国連邦自動車安全基準）Ｎｏ．３０２やＪＩＳ Ｄ １２０１：１９９８などの車両用内装材の燃焼性試験規格をクリアする高度な難燃性を有し、それゆえ車両用内装材はもちろん、インテリア資材としても特に好適に用いることが可能である。 For example, in order to make synthetic leather flame retardant, a flame retardant may be added to the adhesive layer provided between the fibrous base material and the skin layer. In this case, the adhesive layer is formed by drying a resin liquid (adhesive layer forming composition) containing a flame retardant, but adhesive liquid containing diorganyl phosphinate as a flame retardant is used for a long time. This may increase the viscosity of the adhesive, making it difficult to process, and furthermore, the precipitation of flame retardant aggregates may occur. As a result, there was a problem in that the adhesive effect of the adhesive layer in the resulting flame-retardant synthetic leather was reduced, and the flame retardance of the flame-retardant synthetic leather was further reduced. Therefore, in order to deal with such problems, the present inventors conducted studies and found that potassium sulfate and/or sulfuric acid were added to a flame retardant composition containing a specified dialkyl phosphinate as a diorganyl phosphinate. By further adding calcium, even when the flame retardant composition is mixed with a resin liquid, thickening is suppressed and it can be used for a long period of time, and precipitation of flame retardant aggregates is significantly suppressed or prevented. The present inventors have discovered that it is possible to provide an excellent flame-retardant synthetic leather that achieves long-term processing stability and, as a result, does not suffer from processing defects such as a decrease in adhesion or a decrease in flame retardancy. Therefore, according to the flame-retardant composition according to the embodiment of the present invention, synthetic leather having a high degree of flame retardancy can be produced for a long period of time without impairing the design, appearance quality, or texture without impairing the adhesive properties. can do. Moreover, the flame-retardant synthetic leather manufactured in this way has, for example, FMVSS (Federal Motor Vehicle Safety Standards) No. It has a high level of flame retardancy that passes the combustibility test standards for vehicle interior materials such as 302 and JIS D 1201:1998, and therefore can be particularly suitable for use not only as vehicle interior materials but also as interior materials. It is.
以下、本発明の実施形態に係る難燃性組成物及びそれを用いた難燃性合成皮革についてより詳しく説明するが、これらの説明は、本発明の好ましい実施形態の単なる例示を意図するものであって、本発明をこのような特定の実施形態に限定することを意図するものではない。 Hereinafter, the flame retardant composition and the flame retardant synthetic leather using the same according to the embodiments of the present invention will be explained in more detail, but these explanations are not intended to be mere illustrations of the preferred embodiments of the present invention. However, it is not intended that the invention be limited to these particular embodiments.
［（Ａ）ジアルキルホスフィン酸塩］
本発明の実施形態に係る難燃性組成物は、下記一般式（１）で表されるジアルキルホスフィン酸塩を含む。
The flame retardant composition according to the embodiment of the present invention contains a dialkyl phosphinate represented by the following general formula (1).
一般式（１）において、Ｒ1及びＲ2は互いに同じであるか又は異なっていてもよく、より具体的には、それぞれ独立してメチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル、ｎ－ペンチル、イソペンチル、ｓｅｃ－ペンチル、３－ペンチル、ｔｅｒｔ－ペンチル、ｎ－ヘキシル、２－メチルペンチル、３－メチルペンチル、２，２－ジメチルブチル、及び２，３－ジメチルブチルからなる群より選択することができる。Ｒ1とＲ2の組み合わせとしては、ここに例示した置換基のあらゆる組み合わせを包含するものである。これらのアルキル基を有するホスフィン酸塩を構成するジアルキルホスフィン酸の具体例としては、特に限定されないが、例えば、ジメチルホスフィン酸、エチルメチルホスフィン酸、ジエチルホスフィン酸、メチル－ｎ－プロピルホスフィン酸などを挙げることができる。 In general formula (1), R 1 and R 2 may be the same or different from each other, and more specifically, each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl. , sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, 3-pentyl, tert-pentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, and 2 , 3-dimethylbutyl. The combination of R 1 and R 2 includes all combinations of substituents exemplified herein. Specific examples of the dialkylphosphinic acid constituting the phosphinate having these alkyl groups include, but are not particularly limited to, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, etc. can be mentioned.
一般式（１）において、Ｍは、このようなジアルキルホスフィン酸との間で塩を形成する金属イオンを表すものであって、具体的には、上記のとおりＣａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｆｅ、Ｚｒ、Ｚｎ、Ｃｅ、Ｂｉ、Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ、Ｋ、Ｈ、又はプロトン化窒素塩基を表し、好ましくはＣａ、Ａｌ、Ｓｎ、Ｔｉ又はＺｎである。 In the general formula (1), M represents a metal ion that forms a salt with such a dialkylphosphinic acid, and specifically, as described above, M represents a metal ion such as Ca, Al, Sb, Sn, Ge, etc. , Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or a protonated nitrogen base, preferably Ca, Al, Sn, Ti or Zn.
ここで、プロトン化窒素塩基は、好ましくは、アンモニア、又は第一級、第二級、第三級若しくは第四級アミンのプロトン化した形態のものである。プロトン化窒素塩基は、好ましくは、メラミン、尿素、ビウレット、グアニジン、アルキルグアニジン、アリールグアニジン、ジフェニルグアニジン、ビグアニド、アラントイン、アセトグアナミン、ベンゾグアナミン、トリルトリアゾール、ベンゾトリアゾール、２－アミノ－４－メチルピリミジン、ベンジル尿素、エチレンジメラミン、アセチレン尿素、ヒダントイン、マロン酸アミドアミジン、ジメチル尿素、５，５－ジフェニルヒダントイン、Ｎ，Ｎ’－ジフェニル尿素、エチレンビス－５－トリアゾン、グリシン無水物、テトラメチル尿素、トリエタノールアミン、メラミンの縮合体、例えばメレム、メラム若しくはメロン、又はこの種のより高度に縮合された化合物のプロトン化した形態のものである。 The protonated nitrogen base here is preferably ammonia or a protonated form of a primary, secondary, tertiary or quaternary amine. Protonated nitrogen bases are preferably melamine, urea, biuret, guanidine, alkylguanidine, arylguanidine, diphenylguanidine, biguanide, allantoin, acetoguanamine, benzoguanamine, tolyltriazole, benzotriazole, 2-amino-4-methylpyrimidine, Benzyl urea, ethylene dimelamine, acetylene urea, hydantoin, malonamide amidine, dimethyl urea, 5,5-diphenylhydantoin, N,N'-diphenyl urea, ethylene bis-5-triazone, glycine anhydride, tetramethyl urea, Triethanolamine, condensates of melamine, such as melem, melam or melon, or protonated forms of more highly condensed compounds of this type.
ｍは、Ｍで表される金属のイオン価を表すものであって、１～４の整数であり、好ましくは２又は３である。 m represents the ionic valence of the metal represented by M, and is an integer of 1 to 4, preferably 2 or 3.
ジアルキルホスフィン酸塩の具体例としては、特に限定されないが、ジメチルホスフィン酸カルシウム、ジメチルホスフィン酸アルミニウム、ジメチルホスフィン酸スズ、ジメチルホスフィン酸チタン、ジメチルホスフィン酸亜鉛、エチルメチルホスフィン酸カルシウム、エチルメチルホスフィン酸アルミニウム、エチルメチルホスフィン酸スズ、エチルメチルホスフィン酸チタン、エチルメチルホスフィン酸亜鉛、ジエチルホスフィン酸カルシウム、ジエチルホスフィン酸アルミニウム、ジエチルホスフィン酸スズ、ジエチルホスフィン酸チタン、ジエチルホスフィン酸亜鉛、メチル－ｎ－プロピルホスフィン酸カルシウム、メチル－ｎ－プロピルホスフィン酸アルミニウム、メチル－ｎ－プロピルホスフィン酸スズ、メチル－ｎ－プロピルホスフィン酸チタン、及びメチル－ｎ－プロピルホスフィン酸亜鉛からなる群より選択される少なくとも１種を挙げることができる。 Specific examples of dialkylphosphinates include, but are not limited to, calcium dimethylphosphinate, aluminum dimethylphosphinate, tin dimethylphosphinate, titanium dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, and ethylmethylphosphinate. Aluminum, tin ethylmethylphosphinate, titanium ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, tin diethylphosphinate, titanium diethylphosphinate, zinc diethylphosphinate, methyl-n-propyl At least one member selected from the group consisting of calcium phosphinate, aluminum methyl-n-propylphosphinate, tin methyl-n-propylphosphinate, titanium methyl-n-propylphosphinate, and zinc methyl-n-propylphosphinate. can be mentioned.
上記のジアルキルホスフィン酸塩は、当業者に公知の任意の適切な方法によって製造してもよいし又は商業的に入手することも可能である。例えば、ジアルキルホスフィン酸塩は、水溶液中において、対応するジアルキルホスフィン酸と、Ｃａ、Ａｌ、Ｓｎ、Ｔｉ、Ｚｎ等の金属の炭酸塩、水酸化物又は酸化物とを反応させることにより製造することが可能である。得られるジアルキルホスフィン酸塩は、本質的にモノマー性化合物であるが、反応条件によってポリマー性化合物も形成し得る。したがって、本明細書において「ジアルキルホスフィン酸塩」という場合には、ジアルキルホスフィン酸塩のモノマーだけでなく、ポリマーをも包含するものである。 The dialkyl phosphinates described above may be prepared by any suitable method known to those skilled in the art or may be obtained commercially. For example, a dialkyl phosphinate can be produced by reacting the corresponding dialkyl phosphinic acid with a carbonate, hydroxide, or oxide of a metal such as Ca, Al, Sn, Ti, or Zn in an aqueous solution. is possible. The resulting dialkyl phosphinates are essentially monomeric compounds, but polymeric compounds may also be formed depending on the reaction conditions. Therefore, in the present specification, the term "dialkyl phosphinate" includes not only dialkyl phosphinate monomers but also polymers.
一般式（１）で表されるジアルキルホスフィン酸塩は、上記のとおり１種を単独で用いてもよいし又は２種以上を組み合わせて用いてもよい。２種以上を組み合わせて用いる場合、一般式（１）に包含されるジアルキルホスフィン酸塩のうち任意の２種以上の組み合わせが可能である。特に限定されないが、例えば、先に例示したジアルキルホスフィン酸塩（ジメチルホスフィン酸カルシウム、ジメチルホスフィン酸アルミニウム、ジメチルホスフィン酸スズ、ジメチルホスフィン酸チタン、ジメチルホスフィン酸亜鉛、エチルメチルホスフィン酸カルシウム、エチルメチルホスフィン酸アルミニウム、エチルメチルホスフィン酸スズ、エチルメチルホスフィン酸チタン、エチルメチルホスフィン酸亜鉛、ジエチルホスフィン酸カルシウム、ジエチルホスフィン酸アルミニウム、ジエチルホスフィン酸スズ、ジエチルホスフィン酸チタン、ジエチルホスフィン酸亜鉛、メチル－ｎ－プロピルホスフィン酸カルシウム、メチル－ｎ－プロピルホスフィン酸アルミニウム、メチル－ｎ－プロピルホスフィン酸スズ、メチル－ｎ－プロピルホスフィン酸チタン、及びメチル－ｎ－プロピルホスフィン酸亜鉛からなる群より選択される少なくとも１種）を主成分（第１のジアルキルホスフィン酸塩）とし、当該主成分と、副成分としての第２のジアルキルホスフィン酸塩を組み合わせてもよい。ここで、本明細書において「主成分」とは、当該主成分を構成する１つ又は複数の化合物をジアルキルホスフィン酸塩全体の質量に対して５０％超の割合で含むことを意味するものである。例えば、第１のジアルキルホスフィン酸塩（主成分）の含有量は、ジアルキルホスフィン酸塩全体（すなわち第１のジアルキルホスフィン酸塩及び第２のジアルキルホスフィン酸塩の合計質量）に対して６５質量％以上、７０質量％以上、８０質量％以上、８５質量％以上又は９０質量％以上であってもよい。上限は特に限定されないが、第１のジアルキルホスフィン酸塩（主成分）の含有量は、例えば、ジアルキルホスフィン酸塩全体に対して９９．９質量％以下、９９質量％以下又は９３質量％以下であってもよい。 The dialkyl phosphinate represented by the general formula (1) may be used singly or in combination of two or more as described above. When using two or more types in combination, any two or more types of dialkyl phosphinates included in general formula (1) can be combined. Examples include, but are not limited to, the dialkylphosphinates listed above (calcium dimethylphosphinate, aluminum dimethylphosphinate, tin dimethylphosphinate, titanium dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, ethylmethylphosphine). Aluminum acid, tin ethylmethylphosphinate, titanium ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, tin diethylphosphinate, titanium diethylphosphinate, zinc diethylphosphinate, methyl-n- At least one member selected from the group consisting of calcium propylphosphinate, aluminum methyl-n-propylphosphinate, tin methyl-n-propylphosphinate, titanium methyl-n-propylphosphinate, and zinc methyl-n-propylphosphinate. species) as the main component (first dialkyl phosphinate), and the main component may be combined with a second dialkyl phosphinate as a subcomponent. Here, the term "main component" as used herein means that one or more compounds constituting the main component are contained in a proportion of more than 50% based on the total mass of the dialkyl phosphinate. be. For example, the content of the first dialkyl phosphinate (main component) is 65% by mass with respect to the entire dialkyl phosphinate (i.e., the total mass of the first dialkyl phosphinate and the second dialkyl phosphinate). The content may be 70% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more. The upper limit is not particularly limited, but the content of the first dialkyl phosphinate (main component) is, for example, 99.9% by mass or less, 99% by mass or less, or 93% by mass or less based on the entire dialkylphosphinate. There may be.
第２のジアルキルホスフィン酸塩（副成分）としては、上記一般式（１）に包含されかつ第１のジアルキルホスフィン酸塩（主成分）とは異なる任意のジアルキルホスフィン酸塩であってよく特に限定されないが、例えば、エチルブチルホスフィン酸塩、ジブチルホスフィン酸塩、エチルヘキシルホスフィン酸塩、ブチルヘキシルホスフィン酸塩、及びジヘキシルホスフィン酸塩からなる群より選択される少なくとも１種であってもよい。より具体的には、第２のジアルキルホスフィン酸塩としては、エチルブチルホスフィン酸カルシウム、エチルブチルホスフィン酸アルミニウム、エチルブチルホスフィン酸スズ、エチルブチルホスフィン酸チタン、エチルブチルホスフィン酸亜鉛、ジブチルホスフィン酸カルシウム、ジブチルホスフィン酸アルミニウム、ジブチルホスフィン酸スズ、ジブチルホスフィン酸チタン、ジブチルホスフィン酸亜鉛、エチルヘキシルホスフィン酸カルシウム、エチルヘキシルホスフィン酸アルミニウム、エチルヘキシルホスフィン酸スズ、エチルヘキシルホスフィン酸チタン、エチルヘキシルホスフィン酸亜鉛、ブチルヘキシルホスフィン酸カルシウム、ブチルヘキシルホスフィン酸アルミニウム、ブチルヘキシルホスフィン酸スズ、ブチルヘキシルホスフィン酸チタン、ブチルヘキシルホスフィン酸亜鉛、ジヘキシルホスフィン酸カルシウム、ジヘキシルホスフィン酸アルミニウム、ジヘキシルホスフィン酸スズ、ジヘキシルホスフィン酸チタン、及びジヘキシルホスフィン酸亜鉛からなる群より選択される少なくとも１種であってもよい。 The second dialkyl phosphinate (subcomponent) may be any dialkyl phosphinate that is included in the above general formula (1) and is different from the first dialkyl phosphinate (main component), and is particularly limited. However, for example, at least one selected from the group consisting of ethylbutylphosphinate, dibutylphosphinate, ethylhexylphosphinate, butylhexylphosphinate, and dihexylphosphinate may be used. More specifically, the second dialkylphosphinate includes calcium ethylbutylphosphinate, aluminum ethylbutylphosphinate, tin ethylbutylphosphinate, titanium ethylbutylphosphinate, zinc ethylbutylphosphinate, and calcium dibutylphosphinate. , aluminum dibutylphosphinate, tin dibutylphosphinate, titanium dibutylphosphinate, zinc dibutylphosphinate, calcium ethylhexylphosphinate, aluminum ethylhexylphosphinate, tin ethylhexylphosphinate, titanium ethylhexylphosphinate, zinc ethylhexylphosphinate, butylhexylphosphinic acid Calcium, aluminum butylhexylphosphinate, tin butylhexylphosphinate, titanium butylhexylphosphinate, zinc butylhexylphosphinate, calcium dihexylphosphinate, aluminum dihexylphosphinate, tin dihexylphosphinate, titanium dihexylphosphinate, and dihexylphosphinic acid. It may be at least one selected from the group consisting of zinc.
副成分としての第２のジアルキルホスフィン酸塩の含有量は、任意の適切な量であってよく特に限定されないが、例えば、ジアルキルホスフィン酸塩全体（すなわち第１のジアルキルホスフィン酸塩及び第２のジアルキルホスフィン酸塩の合計質量）に対して、０．１～３０質量％であることが好ましい。第２のジアルキルホスフィン酸塩の含有量をこのような範囲に制御することで、難燃性組成物を樹脂液に混合した場合においても増粘が抑制されて長期間使用することができ、難燃剤凝集物の析出を顕著に抑制又は防止して長期的な加工安定性を実現するとともに、その結果として接着性の低下や難燃性の低下といった加工不良が生じることのない優れた難燃性合成皮革を提供することができるという効果をより確実なものとすることができる。これらの効果をさらに高める観点からは、第２のジアルキルホスフィン酸塩の含有量は、ジアルキルホスフィン酸塩全体に対して０．５質量％以上又は１質量％以上であることがより好ましく、３質量％以上、５質量％以上又は７質量％以上であることがさらに好ましい。一方で、粘度安定性を高めるとともに接着性の低下を防ぐ観点からは、第２のジアルキルホスフィン酸塩の含有量は、ジアルキルホスフィン酸塩全体に対して２５質量％以下又は２０質量％以下であることがより好ましく、１５質量％以下又は１０質量％以下であることがさらに好ましい。したがって、第２のジアルキルホスフィン酸塩の含有量は、例えば、ジアルキルホスフィン酸塩全体に対して１～２０質量％であることがより好ましく、７～１５質量％であることがさらに好ましい。 The content of the second dialkylphosphinate as a subcomponent may be any suitable amount and is not particularly limited, but for example, the content of the entire dialkylphosphinate (i.e., the first dialkylphosphinate and the second The amount is preferably 0.1 to 30% by mass based on the total mass of dialkylphosphinates. By controlling the content of the second dialkyl phosphinate within such a range, even when the flame retardant composition is mixed with the resin liquid, thickening is suppressed and it can be used for a long period of time. Excellent flame retardancy that significantly suppresses or prevents the precipitation of refractory aggregates to achieve long-term processing stability, and as a result does not result in processing defects such as reduced adhesion or flame retardancy. The effect of being able to provide synthetic leather can be made more reliable. From the viewpoint of further enhancing these effects, the content of the second dialkyl phosphinate is more preferably 0.5% by mass or more or 1% by mass or more based on the entire dialkylphosphinate, and 3% by mass or more. % or more, 5% by mass or more, or 7% by mass or more is more preferable. On the other hand, from the viewpoint of increasing viscosity stability and preventing a decrease in adhesive properties, the content of the second dialkyl phosphinate is 25% by mass or less or 20% by mass or less based on the entire dialkylphosphinate. The content is more preferably 15% by mass or less, or even more preferably 10% by mass or less. Therefore, the content of the second dialkyl phosphinate is, for example, more preferably 1 to 20% by mass, and even more preferably 7 to 15% by mass, based on the entire dialkyl phosphinate.
第２のジアルキルホスフィン酸塩は、第１のジアルキルホスフィン酸塩と同様に、当業者に公知の任意の適切な方法によって製造してもよいし又は商業的に入手することも可能である。例えば、第２のジアルキルホスフィン酸塩は、水溶液中において、対応するジアルキルホスフィン酸と、Ｃａ、Ａｌ、Ｓｎ、Ｔｉ、Ｚｎ等の金属の炭酸塩、水酸化物又は酸化物とを反応させることにより製造することが可能である。あるいはまた、第２のジアルキルホスフィン酸塩は、主成分として含まれるジアルキルホスフィン酸塩の製造時に副生成物として生成したものであってもよい。第２のジアルキルホスフィン酸塩は、本質的にモノマー性化合物であるが、反応条件によってポリマー性化合物も形成し得る。したがって、本明細書において「第２のジアルキルホスフィン酸塩」という場合には、ジアルキルホスフィン酸塩のモノマーだけでなく、ポリマーをも包含するものである。 The second dialkyl phosphinate, like the first dialkyl phosphinate, may be prepared by any suitable method known to those skilled in the art or may be obtained commercially. For example, the second dialkyl phosphinate can be prepared by reacting the corresponding dialkyl phosphinic acid with a carbonate, hydroxide, or oxide of a metal such as Ca, Al, Sn, Ti, or Zn in an aqueous solution. It is possible to manufacture. Alternatively, the second dialkyl phosphinate may be produced as a by-product during the production of the dialkyl phosphinate contained as the main component. The second dialkyl phosphinate is an essentially monomeric compound, but polymeric compounds may also be formed depending on the reaction conditions. Therefore, in the present specification, the term "second dialkyl phosphinate" includes not only monomers of dialkyl phosphinate but also polymers.
ジアルキルホスフィン酸塩の粒子径は、任意の適切な値であってよく特に限定されないが、例えば、ジアルキルホスフィン酸塩のメジアン径（ｄ５０：累積体積が５０％に達したときの粒子径）は０．１～１０００μｍであることが好ましい。ここで、本明細書において「ジアルキルホスフィン酸塩の粒子径」とは、一般式（１）に含まれる全てのジアルキルホスフィン酸塩の粒子径を意味するものであり、例えばジアルキルホスフィン酸塩が上記第１及び第２のジアルキルホスフィン酸塩を含む場合には、それらを含むジアルキルホスフィン酸塩全体の粒子径、例えばメジアン径を意味するものである。ジアルキルホスフィン酸塩のメジアン径を０．１～１０００μｍの範囲に制御することで、難燃性組成物を樹脂液に混合した場合においても増粘が抑制されて長期間使用することができ、難燃剤凝集物の析出を顕著に抑制又は防止して長期的な加工安定性を実現するとともに、その結果として接着性の低下や難燃性の低下といった加工不良が生じることのない優れた難燃性合成皮革を提供することができるという効果をより確実なものとすることができる。これらの効果をさらに高める観点からは、ジアルキルホスフィン酸塩のメジアン径は０．５μｍ以上又は１μｍ以上であることがより好ましく、２μｍ以上又は３μｍ以上であることがさらに好ましい。一方で、接着性の低下防止及び難燃性向上の観点からは、ジアルキルホスフィン酸塩のメジアン径は５００μｍ以下又は１００μｍ以下であることがより好ましく、５０μｍ以下又は１０μｍ以下であることがさらに好ましい。したがって、ジアルキルホスフィン酸塩のメジアン径は、例えば１～１００μｍであることがより好ましく、２～１０μｍであることがさらに好ましい。粒子径の制御は、任意の適切な方法によって行うことができる。特に限定されないが、例えば、所定の粒子径を有するジアルキルホスフィン酸塩と硫酸カリウム及び／又は硫酸カルシウムとを混合し、次いで乾式粉砕等を行うことによってジアルキルホスフィン酸塩を所望の粒子径に制御することが可能である。 The particle size of the dialkyl phosphinate may be any appropriate value and is not particularly limited, but for example, the median diameter (d50: particle size when the cumulative volume reaches 50%) of the dialkyl phosphinate is 0. The thickness is preferably .1 to 1000 μm. Here, in this specification, "particle size of dialkyl phosphinate" means the particle size of all dialkyl phosphinates included in general formula (1), and for example, when the dialkyl phosphinate is When the first and second dialkyl phosphinates are included, it means the particle size of the entire dialkyl phosphinate including them, for example, the median diameter. By controlling the median diameter of the dialkyl phosphinate in the range of 0.1 to 1000 μm, even when the flame retardant composition is mixed with the resin liquid, thickening is suppressed and it can be used for a long period of time. Excellent flame retardancy that significantly suppresses or prevents the precipitation of refractory aggregates to achieve long-term processing stability, and as a result does not result in processing defects such as reduced adhesion or flame retardancy. The effect of being able to provide synthetic leather can be made more reliable. From the viewpoint of further enhancing these effects, the median diameter of the dialkylphosphinate is more preferably 0.5 μm or more or 1 μm or more, and even more preferably 2 μm or more or 3 μm or more. On the other hand, from the viewpoint of preventing a decrease in adhesion and improving flame retardancy, the median diameter of the dialkyl phosphinate is more preferably 500 μm or less or 100 μm or less, and even more preferably 50 μm or less or 10 μm or less. Therefore, the median diameter of the dialkylphosphinate is, for example, more preferably 1 to 100 μm, and even more preferably 2 to 10 μm. Control of particle size can be performed by any suitable method. Although not particularly limited, for example, the dialkyl phosphinate may be controlled to have a desired particle size by mixing a dialkyl phosphinate having a predetermined particle size with potassium sulfate and/or calcium sulfate, and then performing dry pulverization or the like. Is possible.
［粒子径の測定］
ジアルキルホスフィン酸塩のメジアン径（ｄ５０）は、以下のようにして決定される。まず、難燃性組成物を所定の非イオン界面活性剤を含有する溶液と混合し、次いで室温で１０分以上超音波にて分散させる。得られた分散液を適切な粒子径分布測定装置を用いて粒度分布を測定し、累積体積が５０％に相当するときの粒子径をｄ５０として決定する。
[Measurement of particle size]
The median diameter (d50) of the dialkylphosphinate is determined as follows. First, a flame retardant composition is mixed with a solution containing a predetermined nonionic surfactant, and then dispersed using ultrasound for 10 minutes or more at room temperature. The particle size distribution of the resulting dispersion is measured using an appropriate particle size distribution measuring device, and the particle size when the cumulative volume corresponds to 50% is determined as d50.
［（Ｂ）硫酸カリウム及び／又は硫酸カルシウム］
本発明の実施形態に係る難燃性組成物は、上記のジアルキルホスフィン酸塩に加えて、硫酸カリウム及び／又は硫酸カルシウムを含む。ジアルキルホスフィン酸塩とともに当該硫酸カリウム及び／又は硫酸カルシウムを含むことにより、難燃性組成物を樹脂液に混合した場合においても増粘が抑制されて長期間使用することができ、難燃剤凝集物の析出を顕著に抑制又は防止して長期的な加工安定性を実現するとともに、その結果として接着層において使用した場合の接着性の低下や難燃性の低下といった加工不良が生じることのない優れた難燃性合成皮革を提供することができる。
[(B) Potassium sulfate and/or calcium sulfate]
The flame retardant composition according to an embodiment of the present invention contains potassium sulfate and/or calcium sulfate in addition to the dialkyl phosphinate described above. By including the potassium sulfate and/or calcium sulfate together with the dialkyl phosphinate, even when the flame retardant composition is mixed with the resin liquid, thickening is suppressed and it can be used for a long period of time, resulting in a flame retardant aggregate. It achieves long-term processing stability by significantly suppressing or preventing the precipitation of It is possible to provide flame-retardant synthetic leather.
硫酸カリウム及び／又は硫酸カルシウムの含有量（合計含有量）は、任意の適切な量であってよく特に限定されないが、例えば、難燃性組成物中に含まれるジアルキルホスフィン酸塩の質量に対して１～１５０００ｐｐｍであることが好ましい。硫酸カリウム及び／又は硫酸カルシウムの含有量をこのような範囲に制御することで、難燃性組成物を樹脂液に混合した場合においても増粘が抑制されて長期間使用することができ、難燃剤凝集物の析出を顕著に抑制又は防止して長期的な加工安定性を実現するとともに、その結果として接着性の低下や難燃性の低下といった加工不良が生じることのない優れた難燃性合成皮革を提供することができるという効果をより確実なものとすることができる。これらの効果をさらに高める観点からは、硫酸カリウム及び／又は硫酸カルシウムの含有量は、難燃性組成物中に含まれるジアルキルホスフィン酸塩の質量に対して１０ｐｐｍ以上、１００ｐｐｍ以上又は１０００ｐｐｍ以上であることがより好ましく、５００ｐｐｍ以上、１０００ｐｐｍ以上、２０００ｐｐｍ以上又は４０００ｐｐｍ以上であることがさらに好ましい。一方で、粘度安定性の向上、接着性の低下防止及び難燃性の向上の観点からは、硫酸カリウム及び／又は硫酸カルシウムの含有量は、難燃性組成物中に含まれるジアルキルホスフィン酸塩の質量に対して１２０００ｐｐｍ以下又は１００００ｐｐｍ以下であることがより好ましく、８５００ｐｐｍ以下又は６０００ｐｐｍ以下であることがさらに好ましい。したがって、硫酸カリウム及び／又は硫酸カルシウムの含有量は、例えば難燃性組成物中に含まれるジアルキルホスフィン酸塩の質量に対して１０００～１００００ｐｐｍであることがより好ましく、４０００～８５００ｐｐｍであることがさらに好ましい。 The content of potassium sulfate and/or calcium sulfate (total content) may be any appropriate amount and is not particularly limited, but for example, the content of potassium sulfate and/or calcium sulfate may be any appropriate amount, but for example, based on the mass of dialkyl phosphinate contained in the flame retardant composition. The amount is preferably 1 to 15,000 ppm. By controlling the content of potassium sulfate and/or calcium sulfate within this range, even when the flame retardant composition is mixed with the resin liquid, thickening is suppressed and it can be used for a long period of time. Excellent flame retardancy that significantly suppresses or prevents the precipitation of refractory aggregates to achieve long-term processing stability, and as a result does not result in processing defects such as reduced adhesion or flame retardancy. The effect of being able to provide synthetic leather can be made more reliable. From the viewpoint of further enhancing these effects, the content of potassium sulfate and/or calcium sulfate is 10 ppm or more, 100 ppm or more, or 1000 ppm or more based on the mass of the dialkyl phosphinate contained in the flame retardant composition. More preferably, it is 500 ppm or more, 1000 ppm or more, 2000 ppm or more, or 4000 ppm or more. On the other hand, from the viewpoint of improving viscosity stability, preventing deterioration of adhesion, and improving flame retardancy, the content of potassium sulfate and/or calcium sulfate should be determined by adjusting the content of dialkyl phosphinate contained in the flame retardant composition. The content is more preferably 12,000 ppm or less or 10,000 ppm or less, and even more preferably 8,500 ppm or less or 6,000 ppm or less. Therefore, the content of potassium sulfate and/or calcium sulfate is more preferably 1000 to 10000 ppm, and more preferably 4000 to 8500 ppm, based on the mass of the dialkyl phosphinate contained in the flame retardant composition. More preferred.
本発明の実施形態に係る難燃性組成物は、上記一般式（１）で表されるジアルキルホスフィン酸塩、並びに硫酸カリウム及び／又は硫酸カルシウムを含んでいればよく、それらに加えて任意選択の添加成分をさらに含んでいてもよい。あるいはまた、当該難燃性組成物は、上記一般式（１）で表されるジアルキルホスフィン酸塩、硫酸カリウム及び／又は硫酸カルシウム、並びに不純物、例えば２％以下、１．５％以下又は１％以下の無機塩（例えば硫酸ナトリウム等）のみから構成されていてもよい。 The flame retardant composition according to the embodiment of the present invention only needs to contain the dialkyl phosphinate represented by the above general formula (1) and potassium sulfate and/or calcium sulfate, and in addition to these, optional It may further contain additional components. Alternatively, the flame retardant composition may contain a dialkyl phosphinate represented by the above general formula (1), potassium sulfate and/or calcium sulfate, and impurities, such as 2% or less, 1.5% or less, or 1% It may be composed only of the following inorganic salts (for example, sodium sulfate, etc.).
＜難燃性合成皮革＞
本発明の実施形態に係る難燃性合成皮革は、繊維質基材の一方の面上に、上で説明した難燃性組成物に加えて樹脂を含む接着層と、表皮層とを順に含むことを特徴としている。先に述べたとおり、当該難燃性組成物は、ジアルキルホスフィン酸塩とともに硫酸カリウム及び／又は硫酸カルシウムを含むことにより、樹脂液に混合した場合においても増粘が抑制されて長期間使用することができ、難燃剤凝集物の析出を顕著に抑制又は防止して長期的な加工安定性を実現することができる。したがって、この難燃性組成物を樹脂とともに接着層に配合することにより、意匠性や外観品位、風合いを損なうことなく高度な難燃性を有する合成皮革を、接着物性を損なうことなく長期的に製造することが可能となる。また、このようにして製造された難燃性合成皮革は、例えば、ＦＭＶＳＳ（米国連邦自動車安全基準）Ｎｏ．３０２やＪＩＳ Ｄ １２０１：１９９８などの車両用内装材の燃焼性試験規格をクリアする高度な難燃性を有し、それゆえ車両用内装材はもちろん、インテリア資材としても特に好適に用いることが可能である。以下、本発明の実施形態に係る難燃性合成皮革の各構成要素についてより詳しく説明する。
<Flame retardant synthetic leather>
The flame-retardant synthetic leather according to the embodiment of the present invention includes, on one side of a fibrous base material, an adhesive layer containing a resin in addition to the flame-retardant composition described above, and a skin layer in this order. It is characterized by As mentioned above, the flame retardant composition contains potassium sulfate and/or calcium sulfate together with the dialkyl phosphinate, so even when mixed with the resin liquid, thickening is suppressed and it can be used for a long period of time. This makes it possible to significantly suppress or prevent the precipitation of flame retardant aggregates and achieve long-term processing stability. Therefore, by blending this flame-retardant composition with resin into the adhesive layer, synthetic leather with a high degree of flame retardancy can be produced for a long time without impairing the design, appearance quality, or texture. It becomes possible to manufacture. Moreover, the flame-retardant synthetic leather manufactured in this way has, for example, FMVSS (Federal Motor Vehicle Safety Standards) No. It has a high level of flame retardancy that passes the combustibility test standards for vehicle interior materials such as 302 and JIS D 1201:1998, and therefore can be particularly suitable for use not only as vehicle interior materials but also as interior materials. It is. Hereinafter, each component of the flame-retardant synthetic leather according to the embodiment of the present invention will be explained in more detail.
［繊維質基材］
本発明の実施形態に係る難燃性合成皮革において用いられる繊維質基材は、特に限定されず、織物、編物若しくは不織布などの繊維質布帛、又は天然皮革などであってよく、目的に応じて適宜選択すればよい。繊維質布帛において繊維の種類は特に限定されるものではなく、天然繊維、再生繊維、半合成繊維、合成繊維など、従来公知の繊維を挙げることができ、これらが２種以上組み合わされていてもよい。また、繊維質布帛に従来公知の溶剤系又は水系の高分子化合物、例えば、ポリウレタン樹脂やその共重合体を塗布又は含浸し、乾式凝固又は湿式凝固させたものを用いることもできる。中でも、強度や加工性の点から、合成繊維からなる編物、特にポリエステル繊維からなる編物（例えばポリエステルニット等）を使用することが好ましい。
[Fibrous base material]
The fibrous base material used in the flame-retardant synthetic leather according to the embodiment of the present invention is not particularly limited, and may be a fibrous fabric such as woven fabric, knitted fabric, or non-woven fabric, or natural leather, depending on the purpose. You can select it as appropriate. The types of fibers used in the fibrous fabric are not particularly limited, and include conventionally known fibers such as natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers, and even if two or more of these are combined. good. It is also possible to use a fibrous fabric coated or impregnated with a conventionally known solvent-based or water-based polymer compound, such as a polyurethane resin or a copolymer thereof, and dry-coagulated or wet-coagulated. Among these, from the viewpoint of strength and processability, it is preferable to use knitted fabrics made of synthetic fibers, particularly knitted fabrics made of polyester fibers (for example, polyester knits, etc.).
［接着層］
本発明の実施形態に係る難燃性合成皮革においては、繊維質基材の一方の面上に、先に説明した難燃性組成物と樹脂を含む接着層が配置される。
[Adhesive layer]
In the flame-retardant synthetic leather according to the embodiment of the present invention, an adhesive layer containing the above-described flame-retardant composition and resin is arranged on one surface of the fibrous base material.
難燃性組成物としては、上で説明した一般式（１）で表されるジアルキルホスフィン酸塩と、（Ｂ）硫酸カリウム及び／又は硫酸カルシウムとを含有する組成物を使用することができる。当該難燃性組成物を接着層において使用することで、接着性の低下を防止するとともに、得られる合成皮革の難燃性を顕著に向上させることが可能である。この難燃性組成物は接着層にのみ配合するということでもよいが、例えば当該接着層に加えて難燃性合成皮革を構成する他の層において配合してもよい。難燃性組成物を接着層以外の層にも配合する場合、特に限定されないが、例えば、接着層と表皮層の間に形成され得る任意選択の中間層において配合することが好ましい。接着層だけでなく、このような中間層にも難燃性組成物を配合することで、難燃性の向上効果をさらに高めることが可能となる。 As the flame retardant composition, a composition containing a dialkyl phosphinate represented by the general formula (1) described above and (B) potassium sulfate and/or calcium sulfate can be used. By using the flame retardant composition in the adhesive layer, it is possible to prevent a decrease in adhesion and to significantly improve the flame retardancy of the resulting synthetic leather. This flame retardant composition may be blended only in the adhesive layer, but may also be blended in other layers constituting the flame retardant synthetic leather in addition to the adhesive layer. When the flame retardant composition is blended into a layer other than the adhesive layer, it is preferably blended into an optional intermediate layer that may be formed between the adhesive layer and the skin layer, for example, although it is not particularly limited. By blending a flame retardant composition not only in the adhesive layer but also in such an intermediate layer, it is possible to further enhance the effect of improving flame retardancy.
接着層における難燃性組成物の含有量は、任意の適切な量であってよく特に限定されないが、例えば、主剤である樹脂１００質量部に対して１～５０質量部であることが好ましい。難燃性組成物の含有量をこのような範囲に制御することで、難燃性組成物中におけるジアルキルホスフィン酸塩の分散性をより高めて凝集物の発生を抑制するとともに、難燃性組成物の粘度安定性を高め、さらには接着性の低下防止や難燃性の向上効果をより確実なものとすることができる。難燃性をさらに高める観点からは、難燃性組成物の含有量は樹脂１００質量部に対して５質量部以上、１０質量部以上又は２０質量部以上であることがより好ましい。一方で、粘度安定性の向上及び接着性の低下防止の観点からは、難燃性組成物の含有量は樹脂１００質量部に対して４０質量％以下であることがより好ましい。したがって、難燃性組成物の含有量は、例えば樹脂１００質量部に対して１０～４０質量部であることがより好ましい。 The content of the flame retardant composition in the adhesive layer may be any appropriate amount and is not particularly limited, but is preferably 1 to 50 parts by weight, for example, based on 100 parts by weight of the resin as the main component. By controlling the content of the flame-retardant composition within such a range, the dispersibility of the dialkyl phosphinate in the flame-retardant composition is further increased and the generation of aggregates is suppressed, and the flame-retardant composition The viscosity stability of the product can be improved, and furthermore, the effects of preventing a decrease in adhesive properties and improving flame retardance can be made more reliable. From the viewpoint of further improving flame retardancy, the content of the flame retardant composition is more preferably 5 parts by mass or more, 10 parts by mass or more, or 20 parts by mass or more based on 100 parts by mass of the resin. On the other hand, from the viewpoint of improving viscosity stability and preventing a decrease in adhesive properties, the content of the flame retardant composition is more preferably 40% by mass or less based on 100 parts by mass of the resin. Therefore, the content of the flame retardant composition is more preferably 10 to 40 parts by weight, for example, per 100 parts by weight of the resin.
樹脂は、特に限定されないが、ポリウレタン樹脂であってよい。ポリウレタン樹脂としては、ポリカーボネート系ポリウレタン、ポリエーテル系ポリウレタン、ポリエステル系ポリウレタン及びこれらの変性物等からなる群より選択される少なくとも１種であってよい。長期耐久性の観点からは、ポリウレタン樹脂としてはポリカーボネート系ポリウレタンが好適である。また、ポリウレタン樹脂は水系又は溶剤系のいずれであってもよい。接着層において用いられるポリウレタン樹脂は、ＪＩＳ Ｋ ６７７２：１９９４に従って測定した硬さが１００％モジュラスで２～２０ＭＰａの範囲内にあるフィルムを形成し得るポリウレタン樹脂であることが好ましく、２～８ＭＰａの範囲内にあるフィルムを形成し得るポリウレタン樹脂であることがより好ましい。本明細書において、接着層において用いられるポリウレタン樹脂の硬さは、以下で説明する架橋剤等により接着層において架橋構造を形成した後の硬さをいうものである。接着層において用いられるポリウレタン樹脂は、得られる難燃性合成皮革の柔軟性をより向上する観点から、後で説明する表皮層において用いられるポリウレタン樹脂と同等であるか又はより柔軟なフィルムを形成し得るポリウレタン樹脂であることが好ましい。これらのポリウレタン樹脂は商業的に入手可能である。 The resin is not particularly limited, but may be a polyurethane resin. The polyurethane resin may be at least one selected from the group consisting of polycarbonate polyurethane, polyether polyurethane, polyester polyurethane, and modified products thereof. From the viewpoint of long-term durability, polycarbonate polyurethane is suitable as the polyurethane resin. Moreover, the polyurethane resin may be either water-based or solvent-based. The polyurethane resin used in the adhesive layer is preferably a polyurethane resin capable of forming a film having a hardness of 100% modulus measured according to JIS K 6772:1994 in the range of 2 to 20 MPa, and preferably in the range of 2 to 8 MPa. More preferably, it is a polyurethane resin capable of forming an inner film. In this specification, the hardness of the polyurethane resin used in the adhesive layer refers to the hardness after forming a crosslinked structure in the adhesive layer using a crosslinking agent or the like as described below. The polyurethane resin used in the adhesive layer should form a film that is equivalent to or more flexible than the polyurethane resin used in the skin layer, which will be explained later, from the perspective of further improving the flexibility of the resulting flame-retardant synthetic leather. It is preferable that the polyurethane resin obtained from These polyurethane resins are commercially available.
接着層には、硬化性向上を目的として、任意選択で架橋剤及び／又は架橋促進剤を添加してもよい。架橋剤及び／又は架橋促進剤は、接着層において用いられるポリウレタン樹脂の種類に応じて適切に選択することができる。特に限定されないが、架橋剤としては、例えば、イソシアネート架橋剤、エポキシ架橋剤、アジリジン架橋剤、カルボジイミド架橋剤、オキサゾリン系架橋剤等が挙げられる。架橋剤は、当該架橋剤に適する架橋促進剤と併用してもよい。架橋剤及び／又は架橋促進剤の含有量は、接着層に求められる強度、柔軟性などを考慮して適宜選択すればよい。 A crosslinking agent and/or a crosslinking accelerator may optionally be added to the adhesive layer for the purpose of improving curability. The crosslinking agent and/or crosslinking accelerator can be appropriately selected depending on the type of polyurethane resin used in the adhesive layer. Although not particularly limited, examples of the crosslinking agent include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, and the like. The crosslinking agent may be used in combination with a crosslinking accelerator suitable for the crosslinking agent. The content of the crosslinking agent and/or crosslinking accelerator may be appropriately selected in consideration of the strength, flexibility, etc. required of the adhesive layer.
接着層の厚み（乾燥後の厚み）は、任意の適切な厚みであってよく特に限定されないが、例えば２０～１００μｍであることが好ましく、３０～８０μｍであることがより好ましい。接着層の厚みをこれらの範囲内に制御することで、十分な弾力性と強度を有する難燃性合成皮革を形成することができる。 The thickness of the adhesive layer (thickness after drying) may be any suitable thickness and is not particularly limited, but is preferably, for example, 20 to 100 μm, more preferably 30 to 80 μm. By controlling the thickness of the adhesive layer within these ranges, flame-retardant synthetic leather having sufficient elasticity and strength can be formed.
［表皮層］
表皮層は、繊維質基材側とは反対側の接着層の面上に配置されるか、又は当該接着層の面上に配置され得る任意選択の中間層の面上に配置される。表皮層としては、合成皮革において一般的に用いられる当業者に公知の任意の表皮層を適用することができる。中でも、耐傷性及び加工性に優れるという点から、表皮層はポリウレタン樹脂を含むことが好ましい。
[Epidermal layer]
The skin layer is placed on the side of the adhesive layer opposite the fibrous substrate side, or on the side of an optional intermediate layer that can be placed on the side of the adhesive layer. As the skin layer, any skin layer commonly used in synthetic leather and known to those skilled in the art can be applied. Among these, it is preferable that the skin layer contains a polyurethane resin from the viewpoint of excellent scratch resistance and processability.
表皮層において用いられるポリウレタン樹脂としては、ポリカーボネート系ポリウレタン、ポリエーテル系ポリウレタン、ポリエステル系ポリウレタン及びこれらの変性物等からなる群より選択される少なくとも１種であってよい。長期耐久性の観点からは、ポリウレタン樹脂としてはポリカーボネート系ポリウレタンが好適である。また、表皮層において用いられるポリウレタン樹脂は水系又は溶剤系のいずれであってもよい。表皮層において用いられるポリウレタン樹脂は、１種を単独で用いてもよいし又は２種以上を組み合わせて用いてもよい。２種以上を組み合わせて用いる場合には、例えば、好適なポリウレタン樹脂であるポリカーボネート系ポリウレタンと、他のポリウレタンとを組み合わせることが好ましい。 The polyurethane resin used in the skin layer may be at least one selected from the group consisting of polycarbonate polyurethane, polyether polyurethane, polyester polyurethane, and modified products thereof. From the viewpoint of long-term durability, polycarbonate polyurethane is suitable as the polyurethane resin. Further, the polyurethane resin used in the skin layer may be either water-based or solvent-based. The polyurethane resins used in the skin layer may be used alone or in combination of two or more. When using two or more types in combination, for example, it is preferable to combine polycarbonate polyurethane, which is a suitable polyurethane resin, with another polyurethane.
表皮層において用いられるポリウレタン樹脂は、ＪＩＳ Ｋ ６７７２：１９９４に従って測定した硬さが１００％モジュラスで２～４０ＭＰａの範囲内にあるフィルムを形成し得るポリウレタンであることが好ましく、３～１０ＭＰａの範囲内にあるフィルムを形成し得るポリウレタンであることがより好ましい。本明細書において、表皮層において用いられるポリウレタン樹脂の硬さは、以下で説明する架橋剤等により表皮層において架橋構造を形成した後の硬さをいうものである。これらのポリウレタン樹脂は商業的に入手可能である。 The polyurethane resin used in the skin layer is preferably a polyurethane that can form a film with a hardness of 100% modulus measured according to JIS K 6772:1994 in the range of 2 to 40 MPa, and preferably in the range of 3 to 10 MPa. More preferably, it is a polyurethane that can form a film. In this specification, the hardness of the polyurethane resin used in the skin layer refers to the hardness after forming a crosslinked structure in the skin layer using a crosslinking agent or the like as described below. These polyurethane resins are commercially available.
表皮層の膜強度を高める観点からは、表皮層は架橋構造を有することが好ましい。架橋構造を形成するために表皮層に含まれ得る架橋剤としては、特に限定されず、従来公知の任意の適切な架橋剤であってよい。例えば、架橋剤としては、イソシアネート架橋剤、エポキシ架橋剤、アジリジン架橋剤、カルボジイミド架橋剤、オキサゾリン系架橋剤等が挙げられる。 From the viewpoint of increasing the membrane strength of the skin layer, it is preferable that the skin layer has a crosslinked structure. The crosslinking agent that may be included in the skin layer to form the crosslinked structure is not particularly limited, and may be any suitable crosslinking agent known in the art. For example, examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, and the like.
表皮層は、さらに他の成分を含んでいてもよい。上記の架橋剤以外に表皮層に含まれ得る他の成分としては、例えば、架橋促進剤、着色剤、光輝剤（例えば、パール剤、メタリック顔料等）、耐光安定剤、紫外線吸収剤、酸化防止剤、感触向上剤、成膜助剤、難燃剤、及び発泡剤等からなる群より選択される少なくとも１種が挙げられる。 The epidermal layer may further contain other components. In addition to the above-mentioned crosslinking agents, other components that may be included in the skin layer include crosslinking accelerators, colorants, brightening agents (e.g., pearlescent agents, metallic pigments, etc.), light stabilizers, ultraviolet absorbers, and antioxidants. At least one selected from the group consisting of additives, feel improvers, film-forming aids, flame retardants, foaming agents, and the like.
着色剤としては、例えば、ウレタン系樹脂粒子、アクリル系樹脂粒子、及びシリコーン系樹脂粒子等からなる群より選択される有機樹脂微粒子に着色剤を含んでなる着色有機樹脂微粒子などが挙げられる。例えば、表皮層が着色剤を含有することで、得られる難燃性合成皮革の意匠性を向上させことが可能である。 Examples of the colorant include colored organic resin fine particles containing a colorant in organic resin fine particles selected from the group consisting of urethane resin particles, acrylic resin particles, silicone resin particles, and the like. For example, when the skin layer contains a colorant, it is possible to improve the design of the resulting flame-retardant synthetic leather.
表皮層の厚み（乾燥後の厚み）は、目的に応じて適宜選択すればよい。特に限定されないが、一般的には、強度及び外観の観点から、表皮層の厚みは１０～５０μｍであることが好ましく、１０～３０μｍであることがより好ましい。 The thickness of the epidermis layer (thickness after drying) may be appropriately selected depending on the purpose. Although not particularly limited, generally from the viewpoint of strength and appearance, the thickness of the skin layer is preferably 10 to 50 μm, more preferably 10 to 30 μm.
本発明の実施形態に係る難燃性合成皮革は、繊維質基材、接着層及び表皮層に加えて、本発明の効果を損なわない限りにおいて、他の層を含んでいてもよい。他の層としては、例えば、中間層及び表面処理層等が挙げられる。以下、これらの層についてより詳しく説明する。 In addition to the fibrous base material, the adhesive layer, and the skin layer, the flame-retardant synthetic leather according to the embodiment of the present invention may contain other layers as long as the effects of the present invention are not impaired. Examples of other layers include an intermediate layer and a surface treatment layer. These layers will be explained in more detail below.
［中間層］
本発明の実施形態に係る難燃性合成皮革は、表皮層の強度をさらに向上させたり、難燃性合成皮革の柔軟性及び／又はクッション性を向上させたり等の目的に応じて、表皮層と接着層との間に任意選択で中間層を含んでいてもよい。
[Middle layer]
The flame-retardant synthetic leather according to the embodiment of the present invention can be used in a skin layer according to the purpose of further improving the strength of the skin layer or improving the flexibility and/or cushioning properties of the flame-retardant synthetic leather. An optional intermediate layer may be included between the adhesive layer and the adhesive layer.
中間層に含まれる成分は特に限定されないが、強度及び柔軟性の観点からは、中間層はポリウレタン樹脂を含むことが好ましい。中間層において用いられるポリウレタン樹脂についても、表皮層において用いられるポリウレタン樹脂と同様に、水系又は溶剤系のいずれであってもよい。中間層において用いられるポリウレタン樹脂は、ＪＩＳ Ｋ ６７７２：１９９４に従って測定した硬さが１００％モジュラスで２～２０ＭＰａの範囲内にあるフィルムを形成し得るポリウレタンであることが好ましく、３～１０ＭＰａの範囲内にあるフィルムを形成し得るポリウレタンであることがより好ましい。中間層は、クッション性向上などの目的で、気泡を内包する樹脂、例えば、気泡を内包するポリウレタン樹脂を含むものであってもよい。上記のポリウレタン樹脂はいずれも商業的に入手可能である。 The components contained in the intermediate layer are not particularly limited, but from the viewpoint of strength and flexibility, it is preferable that the intermediate layer contains a polyurethane resin. Similarly to the polyurethane resin used in the skin layer, the polyurethane resin used in the intermediate layer may be either water-based or solvent-based. The polyurethane resin used in the intermediate layer is preferably a polyurethane capable of forming a film having a hardness of 100% modulus measured according to JIS K 6772:1994 in the range of 2 to 20 MPa, and preferably in the range of 3 to 10 MPa. More preferably, it is a polyurethane that can form a film. The intermediate layer may include a resin containing bubbles, for example, a polyurethane resin containing bubbles, for the purpose of improving cushioning properties. All of the above polyurethane resins are commercially available.
中間層は、さらに、成膜助剤、顔料、難燃剤、充填材、老化防止剤、紫外線吸収剤、芳香剤等の成分を含んでいてもよい。とりわけ、本発明の実施形態に係る難燃性合成皮革が中間層を含む場合には、中間層は難燃剤として、上で説明した一般式（１）で表されるジアルキルホスフィン酸塩と、（Ｂ）硫酸カリウム及び／又は硫酸カルシウムとを含有する難燃性組成物を含むことが好ましい。接着層と中間層の両方で当該難燃性組成物を含むことで、得られる合成皮革の難燃性をより顕著に向上させることができる。 The intermediate layer may further contain components such as film-forming aids, pigments, flame retardants, fillers, anti-aging agents, ultraviolet absorbers, and fragrances. In particular, when the flame-retardant synthetic leather according to the embodiment of the present invention includes an intermediate layer, the intermediate layer contains a dialkyl phosphinate represented by the general formula (1) explained above as a flame retardant, and ( B) It is preferable to include a flame retardant composition containing potassium sulfate and/or calcium sulfate. By including the flame retardant composition in both the adhesive layer and the intermediate layer, the flame retardance of the resulting synthetic leather can be more significantly improved.
中間層の厚み（乾燥後の厚み）は、目的に応じて適宜調整することができる。一般的には、中間層の厚みは３０～３５０μｍであることが好ましく、５０～２５０μｍであることがより好ましい。 The thickness of the intermediate layer (thickness after drying) can be adjusted as appropriate depending on the purpose. Generally, the thickness of the intermediate layer is preferably 30 to 350 μm, more preferably 50 to 250 μm.
［表面処理層］
本発明の実施形態に係る難燃性合成皮革は、外観品位等の向上の観点から、表皮層の表面に、任意選択で表面処理層をさらに設けてもよい。
[Surface treatment layer]
The flame-retardant synthetic leather according to the embodiment of the present invention may optionally further include a surface treatment layer on the surface of the skin layer from the viewpoint of improving the appearance quality and the like.
表面処理層に含まれる成分は特に限定されず、目的に応じて任意の樹脂を用いることができる。表面処理層において用いられる樹脂としては、例えば、ポリウレタン、アクリル、エラストマー等が好ましく、ポリウレタンがより好ましい。表面処理層は、さらに、架橋剤、有機フィラー、滑剤、及び難燃剤等を含んでいてもよい。例えば、表面処理層に有機フィラー、滑剤等を含めることで、表皮層に滑らかな感触が付与され、耐摩耗性をより向上させることができる。 The components contained in the surface treatment layer are not particularly limited, and any resin can be used depending on the purpose. As the resin used in the surface treatment layer, for example, polyurethane, acrylic, elastomer, etc. are preferable, and polyurethane is more preferable. The surface treatment layer may further contain a crosslinking agent, an organic filler, a lubricant, a flame retardant, and the like. For example, by including an organic filler, a lubricant, etc. in the surface treatment layer, a smooth feel can be imparted to the skin layer, and the wear resistance can be further improved.
［難燃性合成皮革の製造］
本発明の実施形態に係る難燃性合成皮革は、当業者に公知の任意の適切な方法によって製造することが可能である。例えば、まず、離型層を有する仮支持体の離型層表面に、ポリウレタン樹脂等の樹脂を含む表皮層形成用組成物を、例えば、密閉式又は開放式のコーティングヘッド塗工装置を用いて乾燥後の表皮層の厚みが所望の厚みとなるような塗布量にて塗布し、次いで加熱乾燥、例えば熱風乾燥することにより仮支持体の離型層上に表皮層を形成する。難燃性合成皮革が中間層を含む場合、形成された表皮層の表面に、好ましくはポリウレタン樹脂を含む中間層形成用組成物を、同様に密閉式又は開放式のコーティングヘッド塗工装置を用いて乾燥後の中間層の厚みが所望の厚みとなるような塗布量にて塗布し、次いで所定の温度及び時間にわたって加熱乾燥することにより、仮支持体上に表皮層と中間層とを含む積層体を形成することができる。例えば、中間層形成用組成物の塗布及び加熱乾燥を２回以上繰り返すことで、任意の厚さの中間層を形成することも可能である。
[Manufacture of flame-retardant synthetic leather]
Flame-retardant synthetic leather according to embodiments of the present invention can be manufactured by any suitable method known to those skilled in the art. For example, first, a composition for forming a skin layer containing a resin such as a polyurethane resin is applied to the surface of the release layer of a temporary support having a release layer using, for example, a closed-type or open-type coating head coating device. A skin layer is formed on the release layer of the temporary support by coating in an amount such that the skin layer has a desired thickness after drying, and then drying by heating, for example, drying with hot air. When the flame-retardant synthetic leather includes an intermediate layer, an intermediate layer forming composition preferably containing a polyurethane resin is applied onto the surface of the formed skin layer using a closed or open coating head coating device. A laminated layer including a skin layer and an intermediate layer is formed on a temporary support by applying the coating in such an amount that the thickness of the intermediate layer after drying becomes the desired thickness, and then heating and drying for a prescribed temperature and time. can form a body. For example, it is also possible to form an intermediate layer of any thickness by repeating application of the composition for forming an intermediate layer and heating and drying it two or more times.
次に、形成された表皮層又は中間層の仮支持体とは反対側の表面に、例えば、ポリウレタン樹脂等の樹脂、当該樹脂１００質量部に対して１～５０質量部の難燃性組成物、並びに所定量の溶剤（例えばＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）等）及び任意選択の架橋剤を含む接着層形成用組成物を、同様に密閉式又は開放式のコーティングヘッド塗工装置を用いて乾燥後の接着層の厚みが所望の厚みとなるような塗布量にて塗布し、所定の温度及び時間にわたって加熱乾燥することにより接着層形成用塗布液層を形成して、難燃性合成皮革形成用の積層体を得る。ここで、使用する難燃性組成物は、事前に乾式粉砕等を行うことによってジアルキルホスフィン酸塩を所望の粒子径に制御しておくことが好ましい。 Next, on the surface of the formed skin layer or intermediate layer opposite to the temporary support, for example, a resin such as a polyurethane resin, and 1 to 50 parts by mass of a flame retardant composition per 100 parts by mass of the resin are applied. , and a predetermined amount of a solvent (for example, N,N-dimethylformamide (DMF), etc.) and an optional crosslinking agent, using a closed or open coating head coating device. After drying, the adhesive layer is coated in an amount such that the thickness of the adhesive layer becomes the desired thickness, and then heated and dried for a predetermined temperature and time to form a coating liquid layer for forming an adhesive layer. A laminate for forming leather is obtained. Here, in the flame retardant composition used, it is preferable to control the dialkyl phosphinate to a desired particle size by performing dry pulverization or the like in advance.
次に、得られた難燃性合成皮革形成用の積層体の接着層形成用塗布液層と繊維質基材とが接するようにして熱圧着を行い、接着層形成用塗布液層に含まれる樹脂を反応硬化させることにより、接着層の形成と、接着層と繊維質基材の密着とを同時に行う。硬化反応のための加熱温度及び加熱時間は、接着層形成用塗布液層に含まれる接着剤としての樹脂の種類により適宜適切な条件を選択することができる。一般的には、加熱温度は３０～８０℃の範囲であることが好ましく、加熱時間は１２～７２時間の範囲であることが好ましい。熱圧着を行う際は、ロールニップ装置等の公知の装置により、加熱温度を１００～１５０℃の範囲に制御してラミネートを行うことが好ましい。また、繊維質基材が少なくとも片面に起毛を有する場合、起毛を有する側を接着層形成用塗布液層と密着させることが好ましい。このようにすることで繊維質基材の起毛繊維が接着層形成用塗布液層に侵入するため、その状態で接着層を硬化することで繊維質基材と接着層との密着性をより向上させることが可能となる。 Next, thermocompression bonding is performed such that the coating liquid layer for forming an adhesive layer of the obtained laminate for forming flame-retardant synthetic leather is in contact with the fibrous base material, so that the coating liquid layer for forming an adhesive layer is By reaction-curing the resin, the formation of the adhesive layer and the adhesion of the adhesive layer to the fibrous base material are simultaneously performed. The heating temperature and heating time for the curing reaction can be appropriately selected depending on the type of resin as the adhesive contained in the adhesive layer forming coating liquid layer. Generally, the heating temperature is preferably in the range of 30 to 80°C, and the heating time is preferably in the range of 12 to 72 hours. When carrying out thermocompression bonding, it is preferable to perform lamination by controlling the heating temperature in the range of 100 to 150° C. using a known device such as a roll nip device. Furthermore, when the fibrous base material has naps on at least one side, it is preferable that the side with the naps is brought into close contact with the coating liquid layer for forming an adhesive layer. By doing this, the raised fibers of the fibrous base material invade the coating liquid layer for forming the adhesive layer, and by curing the adhesive layer in this state, the adhesion between the fibrous base material and the adhesive layer is further improved. It becomes possible to do so.
最後に、仮支持体を剥離することにより、本発明の実施形態に係る難燃性合成皮革を得ることができる。表面処理層を形成する場合には、水系エマルジョン樹脂を含む表面処理剤組成物や有機溶剤系表面処理剤組成物を、表皮層の表面に塗布することで形成することが可能である。 Finally, by peeling off the temporary support, the flame-retardant synthetic leather according to the embodiment of the present invention can be obtained. When forming a surface treatment layer, it can be formed by applying a surface treatment agent composition containing a water-based emulsion resin or an organic solvent-based surface treatment agent composition to the surface of the skin layer.
本発明の実施形態に係る難燃性合成皮革は、意匠性や外観品位、風合いを損なうことなく高度な難燃性を達成することが可能である。このため、自動車用内装材、鉄道車両内装部品、航空機内装部品はもちろんのこと、家具等のインテリア資材としても特に好適に用いることが可能である。 The flame-retardant synthetic leather according to the embodiment of the present invention can achieve a high degree of flame retardancy without impairing design, appearance quality, or texture. Therefore, it can be particularly suitably used not only as interior materials for automobiles, interior parts for railway vehicles, and interior parts for aircraft, but also as interior materials for furniture and the like.
以下、実施例によって本発明をより詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
本実施例では、本発明の実施形態に係る難燃性組成物を種々の条件下で製造し、得られた難燃性組成物を用いて難燃性合成皮革を製造して、それらの種々の特性について調べた。 In this example, flame-retardant compositions according to embodiments of the present invention were manufactured under various conditions, and flame-retardant synthetic leather was manufactured using the obtained flame-retardant compositions. We investigated the characteristics of
［実施例１］
［難燃性組成物の製造］
まず、粒子径（ｄ５０）２０μｍのジアルキルホスフィン酸アルミニウム（主成分：ジエチルホスフィン酸アルミニウム、及び副成分：２質量％のエチルブチルホスフィン酸アルミニウム）に硫酸カリウムを４０００ｐｐｍ混合し、次いで粒子径（ｄ５０）が４μｍになるまで乾式粉砕（（株）セイシン企業製、超微粉卓上型ラボジェットミル）することにより難燃性組成物を得た。難燃性組成物中に含まれる各成分の含有量は表１に示すとおりである。
[Example 1]
[Manufacture of flame retardant composition]
First, 4000 ppm of potassium sulfate was mixed with aluminum dialkyl phosphinate (main component: aluminum diethylphosphinate, and subcomponent: 2% by mass aluminum ethylbutylphosphinate) with a particle size (d50) of 20 μm, and then the particle size (d50) A flame-retardant composition was obtained by dry pulverizing (Ultrafine desktop Lab Jet Mill, manufactured by Seishin Enterprise Co., Ltd.) until the particle diameter was 4 μm. The content of each component contained in the flame retardant composition is as shown in Table 1.
［粒子径（ｄ５０）の測定］
粒子径（ｄ５０）の測定は、具体的には以下のようにして行った。まず、難燃性組成物１ｇをＨＬＢ値が約１３の非イオン界面活性剤を１％含有する溶液１８ｇと混合し、次いで室温（２５℃）で１５分間超音波にて分散させた。得られた分散液をレーザ回折／散乱式粒子径分布測定装置（ＨＯＲＩＢＡ製、ＬＡ－９６０Ｖ２）を用いて粒度分布を測定し、累積体積が５０％に相当するときの粒子径をｄ５０として決定した。
[Measurement of particle diameter (d50)]
Specifically, the particle diameter (d50) was measured as follows. First, 1 g of the flame retardant composition was mixed with 18 g of a solution containing 1% of a nonionic surfactant having an HLB value of about 13, and then dispersed using ultrasound for 15 minutes at room temperature (25° C.). The particle size distribution of the obtained dispersion liquid was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by HORIBA, LA-960V2), and the particle size when the cumulative volume corresponded to 50% was determined as d50. .
［難燃性合成皮革の製造］
まず、仮支持体として、表面離型処理され、離型層を有する紋付き離型紙（大日本印刷（株）製、ＤＥ－４１：紙厚平均１４０μｍ）を用いた。次に、下記に示す表皮層形成用組成物を調製するための各成分を、溶剤、着色有機樹脂微粒子及びポリウレタン樹脂の順でビーカーに加え、次いでディスパー分散機（プライミクス（株）製、ホモディスパー２．５型）で１０００ｒｐｍ×１０分以上混合することにより表皮層形成用組成物を得た。
[Manufacture of flame-retardant synthetic leather]
First, as a temporary support, a patterned release paper (manufactured by Dai Nippon Printing Co., Ltd., DE-41, paper thickness average 140 μm) having a surface release treatment and a release layer was used. Next, each component for preparing the composition for forming a skin layer shown below was added to a beaker in the order of solvent, colored organic resin fine particles, and polyurethane resin, and then a Disper disperser (manufactured by Primix Co., Ltd., Homo Disper 2.5 type) at 1000 rpm for 10 minutes or more to obtain a composition for forming an epidermal layer.
（表皮層形成用組成物）
・１００％モジュラスが５ＭＰａの無黄変型ポリカーボネート系ポリウレタン樹脂（ＤＩＣ（株）製、クリスボンＮＹ３２７）
１００質量部
・着色有機樹脂微粒子（ＤＩＣ（株）製、ダイラック（登録商標）カラーシリーズ）
１８質量部
・溶剤（Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）とイソプロパノール（ＩＰＡ）との質量比８０：２０の混合溶媒）
３６質量部
(Composition for forming epidermal layer)
・Non-yellowing polycarbonate polyurethane resin with 100% modulus of 5 MPa (manufactured by DIC Corporation, Crisbon NY327)
100 parts by mass of colored organic resin fine particles (manufactured by DIC Corporation, Dailac (registered trademark) color series)
18 parts by mass/solvent (mixed solvent of N,N-dimethylformamide (DMF) and isopropanol (IPA) in a mass ratio of 80:20)
36 parts by mass
次に、離型層を備えた離型紙の離型層形成側の表面に、上記の表皮層形成用組成物を、開放式のコーティングヘッド塗工装置を用いて乾燥後の表皮層の厚みが３０μｍとなるような塗布量にて塗布し、次いで１００℃で２分間、熱風乾燥機を用いて塗膜を熱風乾燥することにより、仮支持体である離型紙上に表皮層を形成した。次に、下記に示す接着層形成用組成物を調製するための各成分を、溶剤、難燃性組成物、ポリウレタン樹脂、架橋剤の順でビーカーに加え、次いでディスパー分散機（プライミクス（株）製、ホモディスパー２．５型）で１０００ｒｐｍ×１０分以上混合することにより接着層形成用組成物を得た。 Next, the above composition for forming a skin layer is applied to the surface of the release paper provided with a release layer on the side where the release layer is to be formed, using an open coating head coating device to adjust the thickness of the skin layer after drying. A skin layer was formed on the release paper as a temporary support by applying the coating at a coating amount of 30 μm and then drying the coating film with hot air at 100° C. for 2 minutes using a hot air dryer. Next, each component for preparing the adhesive layer forming composition shown below was added to a beaker in the order of solvent, flame retardant composition, polyurethane resin, and crosslinking agent, and then a Disper dispersion machine (Primix Co., Ltd.) was added to the beaker. A composition for forming an adhesive layer was obtained by mixing the mixture at 1000 rpm for 10 minutes or more using a Homo Disper Model 2.5 (manufactured by Kogyo Co., Ltd.).
（接着層形成用組成物）
・１００％モジュラスが２．５ＭＰａの難黄変型ポリカーボネート系ポリウレタン樹脂（ＤＩＣ（株）製、クリスボンＴＡ２０５ＦＴ）
１００質量部
・表１に記載の難燃性組成物 ３６質量部
・溶剤（ＤＭＦ：Ｎ，Ｎ－ジメチルホルムアミド） ６５質量部
・架橋剤（ＤＩＣ（株）製、バーノック（登録商標）ＤＮ９５０） １０質量部
(Composition for forming adhesive layer)
・Non-yellowing polycarbonate polyurethane resin with 100% modulus of 2.5 MPa (manufactured by DIC Corporation, Crisbon TA205FT)
100 parts by mass・36 parts by mass of the flame retardant composition listed in Table 1・65 parts by mass of solvent (DMF: N,N-dimethylformamide)・Crosslinking agent (manufactured by DIC Corporation, Burnock (registered trademark) DN950) 10 Mass part
形成した表皮層の離型紙とは反対側の表面に、上記の接着層形成用組成物を、開放式のコーティングヘッド塗工装置を用いて乾燥後の接着層の厚みが５０μｍとなるような塗布量にて塗布し、次いで１００℃で２分間乾燥することにより表皮層の離型紙とは反対側の表面に接着層形成用塗布液層を形成して、難燃性合成皮革形成用の積層体を得た。 On the surface of the formed skin layer opposite to the release paper, apply the above adhesive layer forming composition using an open coating head coating device so that the adhesive layer has a thickness of 50 μm after drying. A coating liquid layer for forming an adhesive layer is formed on the surface of the surface layer opposite to the release paper by applying the same amount and drying at 100° C. for 2 minutes to form a laminate for forming flame-retardant synthetic leather. I got it.
次に、得られた難燃性合成皮革形成用の積層体の接着層形成用塗布液層と繊維質基材としてのポリエステルニットとを接触させてロールニップ装置でラミネートした後、巻き取って５０℃で４８時間維持し、接着層形成用塗布液層に含まれるポリウレタン樹脂の硬化反応を進行させることにより、繊維質基材と密着した接着層を形成した。最後に、仮支持体を剥離することにより、繊維質基材の一方の面上に、接着層と表皮層とをこの順で含む実施例１の難燃性合成皮革を得た。 Next, the coating liquid layer for forming the adhesive layer of the obtained laminate for forming flame-retardant synthetic leather and the polyester knit as a fibrous base material were brought into contact with each other and laminated using a roll nip device, and then rolled up and heated at 50°C. This was maintained for 48 hours to advance the curing reaction of the polyurethane resin contained in the adhesive layer forming coating liquid layer, thereby forming an adhesive layer in close contact with the fibrous base material. Finally, the temporary support was peeled off to obtain the flame-retardant synthetic leather of Example 1, which included an adhesive layer and a skin layer in this order on one side of the fibrous base material.
［実施例２～１３］
難燃性組成物における各成分の含有量に加えて、硫酸カリウムを硫酸カルシウムに適宜変更し、さらに粒子径（ｄ５０）（実施例１３は乾式粉砕不実施）を適宜変更したこと以外は実施例１の場合と同様にして、実施例２～１３の難燃性合成皮革を得た。表１を参照すると、各実施例における表皮層及び接着層の塗布量は異なっているものの、乾燥後の各層の厚みは、実施例１の場合と同様に表皮層が３０μｍ、接着層が５０μｍで同じであった。
[Examples 2 to 13]
Examples except that in addition to the content of each component in the flame retardant composition, potassium sulfate was changed to calcium sulfate as appropriate, and the particle size (d50) (dry grinding was not performed in Example 13) was changed as appropriate. In the same manner as in Example 1, flame-retardant synthetic leathers of Examples 2 to 13 were obtained. Referring to Table 1, although the coating amounts of the skin layer and adhesive layer are different in each example, the thickness of each layer after drying is 30 μm for the skin layer and 50 μm for the adhesive layer, as in Example 1. It was the same.
［比較例１～８］
副成分であるエチルブチルホスフィン酸アルミニウムの含有量、並びに硫酸カリウムを含まないか又は他の化合物に変更したこと以外は実施例１の場合と同様にして、比較例１～８の難燃性合成皮革を得た。各比較例において、乾燥後の各層の厚みは表皮層が３０μｍ、接着層が５０μｍであった。
[Comparative Examples 1 to 8]
Flame retardant synthesis of Comparative Examples 1 to 8 was carried out in the same manner as in Example 1, except that the content of aluminum ethylbutylphosphinate, which is a subcomponent, and potassium sulfate were not included or changed to other compounds. Obtained leather. In each comparative example, the thickness of each layer after drying was 30 μm for the skin layer and 50 μm for the adhesive layer.
各実施例及び比較例に関して、下記の各評価方法に基づいて、難燃性組成物の分散性及び粘度安定性、並びに難燃性合成皮革の接着性及び難燃性（燃焼性）を評価した。 Regarding each Example and Comparative Example, the dispersibility and viscosity stability of the flame retardant composition, and the adhesion and flame retardance (flammability) of the flame retardant synthetic leather were evaluated based on the following evaluation methods. .
［分散性の評価］
上で説明した溶剤、難燃性組成物、ポリウレタン樹脂、架橋剤を混合した接着層形成用組成物の樹脂液を黒台紙に膜厚：０．４～０．５ｍｍでコーディングし、面積１０ｃｍ×１５ｃｍに含まれる樹脂液中の凝集物の量を目視観察し、下記基準に従って分散性の合否を評価した。
合格 ：凝集物が５個未満
不合格：凝集物が５個以上
[Evaluation of dispersibility]
The resin liquid of the adhesive layer forming composition mixed with the solvent, flame retardant composition, polyurethane resin, and crosslinking agent described above was coated on a black mount to a film thickness of 0.4 to 0.5 mm, and an area of 10 cm x The amount of aggregates contained in the resin solution per 15 cm was visually observed, and the dispersibility was evaluated according to the following criteria.
Pass: Less than 5 aggregates Fail: 5 or more aggregates
［粘度安定性の評価］
同じ接着層形成用組成物の樹脂液について、混合後３０分以内と７２時間後の樹脂液を２００ｍｌのビーカーに加えて２０℃で静置させた後、粘度計（東機産業（株）製、ＴＶ形粘度計：ＴＶＢ１０Ｍ、スピンドル：Ｍ４（ロータＮｏ．２３）、回転速度：１２ｒｐｍ、温度：２０℃）で粘度を測定した。混合後３０分以内から７２時間後の粘度変化に基づき、下記基準に従って粘度安定性の合否を評価した。
合格 ：５０００ｍＰａ・ｓ未満
不合格：５０００ｍＰａ・ｓ以上
[Evaluation of viscosity stability]
Regarding the resin liquid of the same adhesive layer forming composition, the resin liquid within 30 minutes and 72 hours after mixing was added to a 200 ml beaker and allowed to stand at 20°C. The viscosity was measured using a TV viscometer: TVB10M, spindle: M4 (rotor No. 23), rotation speed: 12 rpm, temperature: 20°C. Based on the change in viscosity from within 30 minutes to 72 hours after mixing, viscosity stability was evaluated according to the following criteria.
Pass: less than 5000mPa・s Fail: 5000mPa・s or more
［接着性の評価］
得られた難燃性合成皮革について、湿熱老化処理（７０℃×９５％ＲＨ×１０週間）にさらした後、ＪＩＳ Ｋ ６８５４－３：１９９９（接着剤－はく離接着強さ試験方法－第３部：Ｔ形はく離）に準拠した試験を行い、難燃性合成皮革の材料破壊強度を測定した。試験に際しては、難燃性合成皮革を用いて幅が２ｃｍの試験片を調製した。また、材料破壊強度が１０Ｎ／ｃｍ以上であれば、十分に高度な水準の接着性を有する難燃性合成皮革であると言え、非常に良好な難燃性合成皮革であると評価することができる。
合格 ：１０Ｎ／ｃｍ以上
不合格：１０Ｎ／ｃｍ未満
[Evaluation of adhesion]
The resulting flame-retardant synthetic leather was subjected to moist heat aging treatment (70°C x 95% RH x 10 weeks) and then tested in accordance with JIS K 6854-3:1999 (Adhesives - Peel adhesion strength test method - Part 3) : T-shaped peeling) was conducted to measure the material fracture strength of the flame-retardant synthetic leather. For the test, a test piece with a width of 2 cm was prepared using flame-retardant synthetic leather. In addition, if the material breaking strength is 10 N/cm or more, it can be said that the flame-retardant synthetic leather has a sufficiently high level of adhesion, and can be evaluated as a very good flame-retardant synthetic leather. can.
Pass: 10N/cm or more Fail: Less than 10N/cm
［難燃性（燃焼性）の評価］
難燃性合成皮革の難燃性（燃焼性）は、ＦＭＶＳＳ（米国連邦自動車安全基準）Ｎｏ．３０２の試験方法に準拠して評価した。具体的には、長さ３５０ｍｍ、巾１００ｍｍに裁断した試験片の端部をガスバーナーで１５秒間接炎させ、着火操作を行い、着火した炎が端部から３８ｍｍの位置に設けた標線を越えてから消火するまでの距離と時間を測定した。タテ方向、ヨコ方向でそれぞれ１０点ずつ測定し、燃焼速度を算出し、タテヨコ計２０回の平均得点を算出した。そして、３点以上を合格とした。
（炎が標線前で消えた場合）
５点：標線から２０ｍｍ以上
４点：１０超～２０ｍｍ未満
３点：１０ｍｍ以下
（炎が標線を超えた場合）
２点：燃焼距離が５０ｍｍ以下かつ燃焼時間６０秒未満
１点：燃焼速度が８０ｍｍ／分未満
０点：燃焼速度が８０ｍｍ／分以上
[Evaluation of flame retardancy (combustibility)]
The flame retardancy (combustibility) of flame-retardant synthetic leather is FMVSS (Federal Motor Vehicle Safety Standard) No. Evaluation was made in accordance with the test method of No. 302. Specifically, the end of a test piece cut to a length of 350 mm and a width of 100 mm was heated with a gas burner for 15 seconds, the ignition was performed, and the ignited flame reached a marked line 38 mm from the end. We measured the distance and time from when the fire was crossed until the fire was extinguished. Measurements were taken at 10 points each in the vertical and horizontal directions, the burning rate was calculated, and the average score for a total of 20 measurements in the vertical and horizontal directions was calculated. A score of 3 or more was considered a pass.
(If the flame goes out in front of the marked line)
5 points: 20 mm or more from the marked line 4 points: More than 10 to less than 20 mm 3 points: 10 mm or less (if the flame exceeds the marked line)
2 points: Burning distance is 50 mm or less and combustion time is less than 60 seconds. 1 point: Burning speed is less than 80 mm/min. 0 points: Burning speed is 80 mm/min or more.
分散性、粘度安定性、接着性及び難燃性の全ての評価が合格であった場合を、使用時に難燃剤凝集物の発生や樹脂液の経時での増粘が少なく、長期的な加工安定性を実現し、加工不良（接着性の低下や難燃性の低下）が生じることがない難燃性組成物及び難燃性合成皮革として評価した。その結果を表１に示す。 If all evaluations of dispersibility, viscosity stability, adhesion, and flame retardancy pass, there is little generation of flame retardant aggregates during use, little thickening of the resin liquid over time, and long-term processing stability. It was evaluated as a flame-retardant composition and flame-retardant synthetic leather that achieves the desired properties and does not cause processing defects (deterioration in adhesion or flame retardancy). The results are shown in Table 1.
表１を参照すると、硫酸カリウムも硫酸カルシウムも含まない主成分のジエチルホスフィン酸アルミニウムと副成分のエチルブチルホスフィン酸アルミニウムから構成される難燃性組成物を用いた比較例１では、難燃性は合格であったものの、分散性、粘度安定性及び接着性のいずれも十分な性能は得られなかった。とりわけ、凝集物の発生や粘度の増加が顕著であった。また、実施例１の場合の硫酸カリウムに代えて硫酸アンモニウムを添加した比較例５では、比較例１の場合と同様に、難燃性は合格であったものの、分散性及び粘度安定性はさらに低下し、これに関連して接着性についてもさらに低下した。一方で、硫酸カリウム及び／又は硫酸カルシウムとは異なる他の化合物を添加した比較例２～４及び６～８では、難燃性、分散性、粘度安定性及び接着性の全てにおいて十分な性能が得られなかった。 Referring to Table 1, in Comparative Example 1 using a flame retardant composition composed of aluminum diethyl phosphinate as a main component and aluminum ethyl butyl phosphinate as a subcomponent, which does not contain potassium sulfate or calcium sulfate, the flame retardant composition was Although the test was passed, sufficient performance was not obtained in terms of dispersibility, viscosity stability, and adhesiveness. In particular, the occurrence of aggregates and increase in viscosity were remarkable. In addition, in Comparative Example 5 in which ammonium sulfate was added in place of potassium sulfate in Example 1, the flame retardance passed the test, as in Comparative Example 1, but the dispersibility and viscosity stability further deteriorated. However, in connection with this, the adhesion properties also decreased further. On the other hand, in Comparative Examples 2 to 4 and 6 to 8, in which compounds other than potassium sulfate and/or calcium sulfate were added, sufficient performance was achieved in all aspects of flame retardancy, dispersibility, viscosity stability, and adhesiveness. I couldn't get it.
これとは対照的に、一般式（１）で表されるジアルキルホスフィン酸塩とともに硫酸カリウム又は硫酸カルシウムを含む難燃性組成物を用いた実施例１～１３では、難燃性、分散性、粘度安定性及び接着性の全てにおいて十分な性能を達成することができた。とりわけ、副成分としての第２のジアルキルホスフィン酸塩を７～１５質量％の範囲で含有し、硫酸カリウム又は硫酸カルシウムを４０００～８５００ｐｐｍの範囲で含有し、さらにジアルキルホスフィン酸塩の粒子径（ｄ５０）を２～１０μｍの範囲内に制御した実施例２、５、９及び１２では、凝集物が全く観察されず、それゆえ高い分散性を達成するとともに、材料破壊強度１３又は１４Ｎ／ｃｍのより高い接着性を示し、さらには難燃性の評価も４又は５点の非常に高い難燃性を達成することができた。 In contrast, in Examples 1 to 13 using flame retardant compositions containing potassium sulfate or calcium sulfate together with the dialkyl phosphinate represented by general formula (1), flame retardancy, dispersibility, It was possible to achieve sufficient performance in both viscosity stability and adhesiveness. In particular, it contains the second dialkylphosphinate as a subcomponent in the range of 7 to 15% by mass, potassium sulfate or calcium sulfate in the range of 4000 to 8500 ppm, and furthermore the particle size of the dialkylphosphinate (d50 ) in Examples 2, 5, 9, and 12, in which the particle diameter was controlled within the range of 2 to 10 μm, no aggregates were observed, and therefore high dispersibility was achieved, as well as a material fracture strength of 13 or 14 N/cm. It exhibited high adhesion and was also able to achieve extremely high flame retardancy, scoring 4 or 5 points.
本発明の難燃組成物を用いれば、樹脂液作成時の難燃剤の凝集物発生や樹脂液の経時での増粘が少なく、長期的な加工安定性を実現できることから、加工欠点のない良好な品位の合皮製品が得られ、合皮製品の加工も経済的に行うことができる。 By using the flame retardant composition of the present invention, there is less occurrence of flame retardant aggregates during the preparation of the resin liquid and less viscosity increase over time of the resin liquid, and long-term processing stability can be achieved. Synthetic leather products of high quality can be obtained, and the processing of synthetic leather products can be carried out economically.
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| PCT/JP2023/015972 WO2023233860A1 (en) | 2022-06-01 | 2023-04-21 | Flame-retardant composition, and flame-retardant synthetic leather using same |
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