JP5738672B2 - Flame retardant resin composition - Google Patents
Flame retardant resin composition Download PDFInfo
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- JP5738672B2 JP5738672B2 JP2011115530A JP2011115530A JP5738672B2 JP 5738672 B2 JP5738672 B2 JP 5738672B2 JP 2011115530 A JP2011115530 A JP 2011115530A JP 2011115530 A JP2011115530 A JP 2011115530A JP 5738672 B2 JP5738672 B2 JP 5738672B2
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- JP
- Japan
- Prior art keywords
- hydroxide
- resin composition
- retardant resin
- zinc
- flame
- 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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- 239000003063 flame retardant Substances 0.000 title claims description 32
- 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 description 31
- 239000011342 resin composition Substances 0.000 title claims description 25
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 11
- 150000003752 zinc compounds Chemical class 0.000 claims description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002657 fibrous material Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 229950003143 basic zinc acetate Drugs 0.000 claims description 3
- JCPDISNOORFYFA-UHFFFAOYSA-H tetrazinc;oxygen(2-);hexaacetate Chemical compound [O-2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JCPDISNOORFYFA-UHFFFAOYSA-H 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 3
- 229940007718 zinc hydroxide Drugs 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229940043825 zinc carbonate Drugs 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 10
- -1 monobutylmaleic acid Chemical class 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000628997 Flos Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- JWPVCFSBPUPIQA-WAYWQWQTSA-N (z)-2-butylbut-2-enedioic acid Chemical compound CCCC\C(C(O)=O)=C\C(O)=O JWPVCFSBPUPIQA-WAYWQWQTSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、自動車内の床及びデッキ部のカーペットや、住宅、事務所等の床部のカーペットなどの繊維製品に裏打ち加工することにより、遮水性や強度とともに難燃性を付与できる難燃性樹脂組成物に関するものである。より詳しくは、重金属を含有したり、ホルムアルデヒドを放散するおそれがある原材料を使用することなく、従前の製品と同等以上の難燃性を付与できる難燃性樹脂組成物に関する。 The present invention provides flame retardancy that can impart flame retardancy as well as water barrier properties and strength by lining textile products such as carpets for floors and decks in automobiles and carpets for floors in houses, offices, etc. The present invention relates to a resin composition. More specifically, the present invention relates to a flame retardant resin composition capable of imparting a flame retardancy equal to or higher than that of a conventional product without using a heavy metal or a raw material that may diffuse formaldehyde.
近年の自動車数の増大や住宅の密集化に伴い、それらの火災に対する対策はきわめて重要である。特に自動車や住宅におけるカーペットなどの内装材についての難燃化の要望は大きく、難燃化技術が種々提案されている。一方、難燃性を有する原材料は何らかの有害性を有しているものが多く、密閉された空間で使用される自動車内装用途においては、有害成分を使用しないか、極力低減させることが強く求められている。 With the recent increase in the number of cars and the concentration of houses, measures against such fires are extremely important. In particular, there is a great demand for flame retardancy of interior materials such as carpets in automobiles and houses, and various flame retarding techniques have been proposed. On the other hand, many flame retardant raw materials have some harmful effects, and in automobile interior applications that are used in sealed spaces, it is strongly required not to use harmful components or to reduce them as much as possible. ing.
特許文献１には三酸化アンチモンを含有する難燃性組成物が開示されている。しかしながら、三酸化アンチモンは不純物として鉛やヒ素を少量ながら含有するため、使用が避けられるようになっている。また、樹脂成分として塩化ビニリデンを含有しているが、塩化ビニリデンは少量のホルムアルヒドを含有するため、この点においても使用が避けられるようになっている。
本発明の課題は、重金属を含有したり、ホルムアルデヒドを放散するおそれがある原材料を使用することなく、従前の製品と同等以上の難燃性を付与できる難燃性樹脂組成物を提供することである。 An object of the present invention is to provide a flame retardant resin composition capable of imparting a flame retardancy equal to or higher than that of a conventional product without using a heavy metal or a raw material that may diffuse formaldehyde. is there.
本発明は少なくとも塩化ビニルと、エチレン、酢酸ビニル、アクリル系単量体から選ばれる１種以上の単量体を重合することによって得られる塩化ビニル系樹脂エマルジョン（ａ）（ただし、ガラス転移点温度が−５〜２５℃のものを除く。）、亜鉛化合物（ｂ）、金属水酸化物（ｃ）を含有することを特徴とする難燃性樹脂組成物である。
The present invention relates to a vinyl chloride resin emulsion (a) obtained by polymerizing at least vinyl chloride and at least one monomer selected from ethylene, vinyl acetate and acrylic monomers (however, glass transition temperature) Is a flame retardant resin composition containing a zinc compound (b) and a metal hydroxide (c).
本発明の難燃性樹脂組成物は、重金属を含有したり、ホルムアルデヒドを放散するおそれがある原材料を使用することなく、従前の製品と同等以上の難燃性を有している。よって、密閉された空間で使用される自動車内装用カーペットなどの繊維材のバッキング用途に適する。 The flame retardant resin composition of the present invention has a flame retardancy equal to or higher than that of a conventional product without using a heavy metal or a raw material that may diffuse formaldehyde. Therefore, it is suitable for backing materials for fiber materials such as automobile interior carpets used in a sealed space.
本発明の難燃性樹脂組成物はバインダー成分として、少なくとも塩化ビニルと、エチレン、酢酸ビニル、アクリル系単量体から選ばれる１種以上の単量体を重合することによって得られる塩化ビニル系樹脂エマルジョン（ａ）を含有する。
アクリル系単量体としては、メチルアクリレート、エチルアクリレート、ｎ−ブチルアクリレート、イソブチルアクリレート、２−エチルヘキシルアクリレート、ｎ−オクチルアクリレート、イソノニルアクリレート、ラウリルアクリレート、ステアリルアクリレートなどのアクリル酸アルキルエステル系単量体、メチルメタクリレート、エチルメタクリレート、ｎ−ブチルメタクリレート、２−エチルヘキシルメタクリレート、ステアリルメタクリレートなどのメタクリル酸アルキルエステル単量体などを単独または２種以上を組み合わせて用いることができる。その他に、スチレン、α−メチルスチレン、ビニルトルエン、エチルビニルベンゼンなどの芳香族ビニル系単量体、プロピオン酸ビニル、バーサチック酸ビニルなどの飽和脂肪酸ビニル系単量体、アクロニトリル、メタクリロニトリルなどのシアン化ビニル系単量体、プロピレン、ブタジエンなどのオレフィン系単量体、モノブチルマレイン酸などのエチレン系ジカルボン酸のモノアルキルエステル、およびこれらのアンモニウム塩もしくはアルカリ金属塩などのエチレン系カルボン酸塩類、アクリルアミド、メタクリルアミド、ジアセトンアクリルアミドなどのエチレン系カルボン酸の酸アミド類、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシメタクリレートなどのエチレン系カルボン酸のヒドロキシアルキルエステル類、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルメタクリレートなどのエチレン系カルボン酸とアミノ基を有するアルコールとのエステル類などを単独または２種以上を組み合わせて用いることができる。
The flame retardant resin composition of the present invention is a vinyl chloride resin obtained by polymerizing at least vinyl chloride and at least one monomer selected from ethylene, vinyl acetate and acrylic monomers as a binder component. Contains emulsion (a).
As acrylic monomers, alkyl acrylate esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, stearyl acrylate, etc. Body, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid alkyl ester monomers such as stearyl methacrylate can be used alone or in combination of two or more. In addition, aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, and ethyl vinyl benzene, saturated fatty acid vinyl monomers such as vinyl propionate and vinyl versatate, acrylonitrile, methacrylonitrile, etc. Vinyl cyanide monomers, olefin monomers such as propylene and butadiene, monoalkyl esters of ethylene dicarboxylic acids such as monobutylmaleic acid, and ethylene carboxylic acids such as ammonium salts and alkali metal salts thereof Salts, acid amides of ethylene carboxylic acids such as acrylamide, methacrylamide and diacetone acrylamide, ethylene carboxylic acids such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxy methacrylate Hydroxyalkyl esters, dimethylaminoethyl methacrylate, esters of an alcohol having an ethylenic carboxylic acid and an amino group such as diethylaminoethyl methacrylate, etc. may be used alone or in combination of two or more.
塩化ビニル系樹脂エマルジョンとして、単量体として塩化ビニルのみを重合して得られるものや、塩化ビニリデンを用いたものは、本願発明には適さない。塩化ビニルのみを重合して得られる樹脂エマルジョンは、単体での難燃性には優れるものの、後述する添加剤との組み合わせによる組成物としての難燃性が十分ではない。また、塩化ビニリデンを用いたものも、同様に後述する添加剤との組み合わせによる組成物としての難燃性が十分ではなく、さらに少量ながらホルムアルデヒドを含有するため、この点からも好ましくない。 As the vinyl chloride resin emulsion, those obtained by polymerizing only vinyl chloride as a monomer or those using vinylidene chloride are not suitable for the present invention. Although the resin emulsion obtained by polymerizing only vinyl chloride is excellent in flame retardancy as a single substance, it does not have sufficient flame retardancy as a composition in combination with additives described later. Similarly, those using vinylidene chloride are also not preferable from this point because they are not sufficiently flame retardant as a composition in combination with additives described later, and contain a small amount of formaldehyde.
亜鉛化合物（ｂ）および金属水酸化物（ｃ）は、本発明の難燃性樹脂組成物に難燃性を付与する目的で用いられる。
亜鉛化合物としては、酸化亜鉛、酢酸亜鉛、塩基性炭酸亜鉛、硫酸亜鉛などが挙げられるが、これらに限定されるものではない。亜鉛化合物の添加量は、前記塩化ビニル系樹脂エマルジョン（ａ）の固形分１００重量部に対して、２〜５０重量部とすることが好ましく、３〜３０重量部配合する事がより好ましい。２重量部未満では樹脂組成物の遅燃効果が十分でなかったり、難燃性能がバラツキやすい。５０重量部を超えると繊維材に加工する際の泡立ち性が低下するおそれがある。
The zinc compound (b) and the metal hydroxide (c) are used for the purpose of imparting flame retardancy to the flame retardant resin composition of the present invention.
Examples of the zinc compound include, but are not limited to, zinc oxide, zinc acetate, basic zinc carbonate, and zinc sulfate. The amount of zinc compound added is preferably 2 to 50 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the solid content of the vinyl chloride resin emulsion (a). If it is less than 2 parts by weight, the slow-flammability effect of the resin composition is not sufficient, and the flame retardancy tends to vary. If it exceeds 50 parts by weight, the foaming property when processing into a fiber material may be reduced.
金属水酸化物（ｃ）としては、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、水酸化マンガン、水酸化鉄、水酸化銅などが挙げられる。中でも好ましいのは水酸化アルミニウムおよび水酸化マグネシウムである。なお、本発明においては、水酸化亜鉛は前記亜鉛化合物（ｂ）とみなす。金属水酸化物の添加量は、前記塩化ビニル系樹脂エマルジョン（ａ）の固形分１００重量部に対して、１０〜５００重量部とすることが好ましく２０〜２５０重量部配合する事がより好ましい。１０重量部未満では樹脂組成物の遅燃効果が十分でなかったり、難燃性能がバラツキやすい。５００重量部を超えると繊維材に加工する際の泡立ち性が低下するおそれがある。 Examples of the metal hydroxide (c) include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, manganese hydroxide, iron hydroxide, and copper hydroxide. Of these, aluminum hydroxide and magnesium hydroxide are preferred. In the present invention, zinc hydroxide is regarded as the zinc compound (b). The addition amount of the metal hydroxide is preferably 10 to 500 parts by weight and more preferably 20 to 250 parts by weight with respect to 100 parts by weight of the solid content of the vinyl chloride resin emulsion (a). If it is less than 10 parts by weight, the slow-flammability effect of the resin composition is not sufficient, and the flame retardancy tends to vary. If it exceeds 500 parts by weight, the foaming property when processing into a fiber material may be reduced.
本発明の難燃性樹脂組成物には前記必須配合成分の他、本発明の優れた効果を妨げない使用範囲において、さらに各種添加剤を配合できる。例えば、ホウ素系化合物、ジルコニウム系化合物などの難燃剤、ブロックイソシアネートの水溶液又は水分散液などの架橋剤が挙げられる。
また、無機充填剤、分散剤、増粘剤、湿潤剤、発泡剤、整泡剤、消泡剤、顔料、染料、可塑剤、老化防止剤、紫外線吸収剤、防腐剤などが使用できる。
In addition to the above essential components, the flame retardant resin composition of the present invention may further contain various additives within the range of use that does not hinder the excellent effects of the present invention. Examples thereof include flame retardants such as boron compounds and zirconium compounds, and crosslinking agents such as aqueous solutions or aqueous dispersions of blocked isocyanates.
Further, inorganic fillers, dispersants, thickeners, wetting agents, foaming agents, foam stabilizers, antifoaming agents, pigments, dyes, plasticizers, anti-aging agents, ultraviolet absorbers, preservatives and the like can be used.
以上のようにして得られた本発明の難燃性樹脂組成物の固形分、ｐＨ及び粘度は、いずれも特に限定されるものではないが、該組成物の沈降安定性等の観点より、一般に固形分は３５〜７０重量％、好ましくは４０〜６０重量％程度、ｐＨは５〜１０、好ましくは６〜１０、粘度（ＢＭ型粘度計、２０℃、１２ｒｐｍ）は１０００〜１５０００ｍＰａ・ｓ、好ましくは１０００〜１００００ｍＰａ・ｓである。 The solid content, pH, and viscosity of the flame-retardant resin composition of the present invention obtained as described above are not particularly limited, but in general, from the viewpoint of sedimentation stability of the composition, etc. The solid content is 35 to 70% by weight, preferably about 40 to 60% by weight, the pH is 5 to 10, preferably 6 to 10, and the viscosity (BM type viscometer, 20 ° C., 12 rpm) is 1000 to 15000 mPa · s, preferably Is 1000 to 10000 mPa · s.
本発明の難燃性樹脂組成物をカーペット生地などの繊維材のバッキング層として用いることにより、難燃性に優れたカーペットを得ることができる。カーペット生地としては、火災時有害ガスの発生のないもの、防縮加工剤などの処理剤としてホルムアルデヒドを生じることのない処理剤を使用したものであれば特に限定されるものではない。例えば、ポリエステル、ポリプロピレン、ナイロン、アクリルなどの合成繊維、羊毛などの天然繊維又はそれらの混紡が挙げられる。また、本発明の難燃性樹脂組成物をバッキング層としたニードルパンチカーペットに対して、さらに成形性、遮水性を向上させるためにポリエチレンなどの熱可塑性樹脂による溶融押し出しラミネートバッキングが施されている場合でも、有効な難燃性を発現する。 By using the flame retardant resin composition of the present invention as a backing layer of a fiber material such as carpet fabric, a carpet having excellent flame retardancy can be obtained. The carpet fabric is not particularly limited as long as it does not generate a harmful gas at the time of fire and uses a processing agent that does not generate formaldehyde as a processing agent such as a shrink-proofing agent. Examples thereof include synthetic fibers such as polyester, polypropylene, nylon, and acrylic, natural fibers such as wool, and blends thereof. Further, the needle punch carpet having the flame retardant resin composition of the present invention as a backing layer is subjected to a melt extrusion laminate backing with a thermoplastic resin such as polyethylene in order to further improve the moldability and water barrier properties. Even in the case, it exhibits effective flame retardancy.
本発明の難燃性樹脂組成物のバッキング層としての塗布量は、固形分で２５〜３００ｇ／ｍ２、好ましくは３０〜２５０ｇ／ｍ２である。塗布量が２５ｇ／ｍ２未満では、風合いが柔らかくなったり難燃性が不十分となるおそれがあり、３００ｇ／ｍ２を超える場合は粉落ちが生じたり、経済的にも好ましくない。
また、このような加工を行なう際、比較的少ない塗布量で均一に塗布するため、樹脂を発泡させた状態で塗布するフロス加工が行なわれるが、本発明の難燃性樹脂組成物は泡立ち性が良好なため、フロス加工にも適する。
The coating amount as a backing layer of the flame retardant resin composition of the present invention is 25 to 300 g / m 2 , preferably 30 to 250 g / m 2 in terms of solid content. If the coating amount is less than 25 g / m 2 , the texture may be soft or the flame retardancy may be insufficient, and if it exceeds 300 g / m 2 , powder falling may occur, which is not economically preferable.
Further, when performing such processing, in order to apply uniformly with a relatively small coating amount, a flossing process is performed in which the resin is foamed. However, the flame-retardant resin composition of the present invention has a foaming property. Is suitable for flossing.
以下、本発明について実施例、参考例及び比較例を挙げてより詳細に説明するが、具体例を示すものであって、特にこれらに限定するものではない。 EXAMPLES Hereinafter, although an Example, a reference example, and a comparative example are given and demonstrated in detail about this invention, a specific example is shown and it does not specifically limit to these.
実施例１
塩化ビニル−アクリル樹脂エマルジョン（日信化学工業社製、固形分４０％、商品名 ビニブラン９００）を固形分で１００重量部、酸化亜鉛（ＪＩＳ Ｋ−１４１０ １種）１０重量部、水酸化アルミニウム（日本軽金属社製、商品名 Ｂ−３０３）１５０重量部、分散剤としてトリポリ燐酸ソーダ（三井化学ファイン社製）１重量部、泡立て剤としてアルキルベンゼンスルホン酸ナトリウム（テイカ社製、商品名 テイカパワーＢＮ−２０６０）４重量部、増粘剤としてキタンサンガム（三晶社製、商品名 KELZAN）１．５重量部を混合し、さらに水を加えて固形分を４０％に調整することにより、実施例１の難燃性樹脂組成物を得た。
Example 1
100 parts by weight of vinyl chloride-acrylic resin emulsion (manufactured by Nissin Chemical Industry Co., Ltd., solid content 40%, trade name Viniblanc 900), 10 parts by weight of zinc oxide (JIS K-1410 type 1), aluminum hydroxide ( Nippon Light Metal Co., Ltd., trade name B-303) 150 parts by weight, sodium tripolyphosphate (manufactured by Mitsui Chemicals Fine) 1 part by weight as a dispersing agent, sodium alkylbenzenesulfonate (trade name, Takeca Power BN- as a foaming agent) 2060) 4 parts by weight, 1.5 parts by weight of Kitansan gum (trade name: KELZAN, manufactured by Sanki Co., Ltd.) as a thickener, and water was added to adjust the solid content to 40%. A flame retardant resin composition was obtained.
実施例２〜１０、比較例１〜７
実施例１で用いた材料の他、塩化ビニル−エチレン−酢酸ビニル樹脂エマルジョンであるスミカフレックスＳ−８５０ＨＱ（住化ケムテックス社製、固形分５０％、商品名）およびスミカフレックスＳ−８３０（住化ケムテックス社製、固形分５０％、商品名）、塩化ビニル樹脂粉末（ヴイテック社製、商品名モンサントＰ−４４０）、酢酸亜鉛、塩基性炭酸亜鉛、水酸化亜鉛、三酸化アンチモン、水酸化マグネシウム（協和化学工業社製）、炭酸カルシウム（三共精粉社製、商品名炭酸カルシウム１級）を用いて、表１、表２記載の配合にて同様に各難燃性樹脂組成物を得た。なお、各樹脂エマルジョンについては固形分を基準とした表記である。
Example 2 to 0, Comparative Examples 1 to 7
In addition to the materials used in Example 1, Sumikaflex S-850HQ (manufactured by Sumika Chemtex Co., Ltd., solid content 50%, trade name) and Sumikaflex S-830 (Sumika) are vinyl chloride-ethylene-vinyl acetate resin emulsions. Chemtex, solid content 50%, trade name), vinyl chloride resin powder (product of Vitec, trade name Monsanto P-440), zinc acetate, basic zinc carbonate, zinc hydroxide, antimony trioxide, magnesium hydroxide ( Each flame-retardant resin composition was obtained in the same manner as in Tables 1 and 2 using calcium carbonate (manufactured by Kyowa Chemical Industry Co., Ltd.) and calcium carbonate (manufactured by Sankyo Seimitsu Co., Ltd., trade name: calcium carbonate grade 1). In addition, about each resin emulsion, it is the description on the basis of solid content.
難燃性
ポリエステル製のニードルパンチカーペット（目付２２０ｇ／ｍ２）に各難燃性樹脂組成物を発泡させて固形分として５０ｇ／ｍ２塗布し、１６０℃雰囲気下で１０分間乾燥した。これを３５０ｍｍ×２００ｍｍに裁断し、２０℃、６５％ＲＨ雰囲気中で２４時間放置したものを試料とした。
自動車内装分野向け難燃規格であるＦＭＶＳＳ−３０２に従い、作成した試料について水平法により燃焼試験を行なった。試験は４点行い、平均燃焼速度および標準偏差（σ）を評価した。
Flame Retardant Each flame retardant resin composition was foamed on a polyester needle punch carpet (weight per unit area: 220 g / m 2 ), applied as a solid content of 50 g / m 2, and dried at 160 ° C. for 10 minutes. The sample was cut into 350 mm × 200 mm and left in a 20 ° C., 65% RH atmosphere for 24 hours as a sample.
In accordance with FMVSS-302, which is a flame retardant standard for the automotive interior field, the prepared sample was subjected to a combustion test by the horizontal method. The test was conducted at four points, and the average burning rate and standard deviation (σ) were evaluated.
貯蔵安定性試験
各難燃性樹脂水性組成物をガラス瓶に入れて４０℃雰囲気下で１ヶ月間保存した後粘度を測定し、保存前の初期粘度と比較して以下のように評価した。
○： 初期粘度から５０％未満の増粘
△： 初期粘度から５０％以上、１００%未満の範囲で増粘
×： 初期粘度から１００%以上の増粘
Storage Stability Test Each flame retardant resin aqueous composition was placed in a glass bottle and stored in a 40 ° C. atmosphere for 1 month, and then the viscosity was measured. The viscosity was evaluated as follows in comparison with the initial viscosity before storage.
○: Less than 50% thickening from initial viscosity Δ: Thickening from initial viscosity to 50% or more and less than 100% ×: Thickening from initial viscosity to 100% or more
フロス加工性試験
各難燃性樹脂水性組成物１５０ｇを１Ｌポリビーカーに量り取り、ハンドミキサー（松下電工社製、形式 ＭＫ−Ｈ３）の目盛りを３にセットして組成物を１２０秒間攪拌し、さらに目盛りを１に切り替えて５秒間攪拌した。すぐに、予め重量を測定しておいた最大容量１４５ｍｌのＰＰカップにすりきりながら移し、１４５ｍｌあたりの組成物の重量を測定することによって発泡比重を測定し、以下のように評価した。
○： 発泡比重が０．３５未満
△： 発泡比重が０．３５以上、０．７０未満
×： 発泡比重が０．７０以上
Floss processability test Weigh 150 g of each flame retardant resin aqueous composition into a 1 L poly beaker, set the scale of a hand mixer (Matsushita Electric Works, Model MK-H3) to 3, and stir the composition for 120 seconds. Further, the scale was switched to 1 and stirred for 5 seconds. Immediately, the foam was transferred to a PP cup having a maximum capacity of 145 ml, which had been weighed in advance, and the specific gravity of foaming was measured by measuring the weight of the composition per 145 ml, and evaluated as follows.
○: Foam specific gravity is less than 0.35 Δ: Foam specific gravity is 0.35 or more and less than 0.70 ×: Foam specific gravity is 0.70 or more
表１、２から明らかなように、実施例の各難燃性樹脂組成物は貯蔵安定性やフロス加工性に優れている。一方、比較例の各難燃性樹脂水性組成物はフロス加工性が劣ったり、難燃性が十分ではなかった。 As is clear from Tables 1 and 2, each flame retardant resin composition of the examples is excellent in storage stability and floss workability. On the other hand, each flame retardant resin aqueous composition of Comparative Example was inferior in floss workability or was not sufficiently flame retardant.
Claims (5)
The fiber material which used the flame-retardant resin composition in any one of Claims 1-4 as a backing use.
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