JP7012007B2 - Fiber treatment agents, manufacturing methods for processed fiber products, and processed fiber products - Google Patents
Fiber treatment agents, manufacturing methods for processed fiber products, and processed fiber products Download PDFInfo
- Publication number
- JP7012007B2 JP7012007B2 JP2018513129A JP2018513129A JP7012007B2 JP 7012007 B2 JP7012007 B2 JP 7012007B2 JP 2018513129 A JP2018513129 A JP 2018513129A JP 2018513129 A JP2018513129 A JP 2018513129A JP 7012007 B2 JP7012007 B2 JP 7012007B2
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- Prior art keywords
- fiber
- treatment agent
- fiber treatment
- meth
- unsaturated monomer
- 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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- 239000000835 fiber Substances 0.000 title claims description 230
- 239000003795 chemical substances by application Substances 0.000 title claims description 132
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000000178 monomer Substances 0.000 claims description 89
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 61
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 55
- 239000003063 flame retardant Substances 0.000 claims description 55
- 229910052698 phosphorus Inorganic materials 0.000 claims description 50
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 47
- 239000011574 phosphorus Substances 0.000 claims description 45
- 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 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- 230000003449 preventive effect Effects 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 15
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 claims description 2
- OKQVTLCUHATGDD-UHFFFAOYSA-N n-(benzotriazol-1-ylmethyl)-2-ethyl-n-(2-ethylhexyl)hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1 OKQVTLCUHATGDD-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- -1 home appliances Substances 0.000 description 53
- 238000000034 method Methods 0.000 description 47
- 238000006116 polymerization reaction Methods 0.000 description 19
- 230000000740 bleeding effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000002265 prevention Effects 0.000 description 10
- 229910052736 halogen Inorganic materials 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 125000004437 phosphorous atom Chemical group 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 239000012776 electronic material Substances 0.000 description 4
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 229910052751 metal Chemical class 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 159000000009 barium salts Chemical class 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 description 2
- IUJGENMYAVALTR-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-phenylbenzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=CC=CC=C1 IUJGENMYAVALTR-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 150000005215 alkyl ethers Chemical class 0.000 description 2
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
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- YSEKNCXYRGKTBJ-UHFFFAOYSA-N dimethyl 2-hydroxybutanedioate Chemical compound COC(=O)CC(O)C(=O)OC YSEKNCXYRGKTBJ-UHFFFAOYSA-N 0.000 description 2
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- 238000004945 emulsification Methods 0.000 description 2
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 description 1
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- MPHUYCIKFIKENX-UHFFFAOYSA-N methyl 2-ethenylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C=C MPHUYCIKFIKENX-UHFFFAOYSA-N 0.000 description 1
- 150000005217 methyl ethers Chemical class 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- BODHJGMCSWVAGR-UHFFFAOYSA-N n,n-diethylethanamine;nitrous acid Chemical compound [O-]N=O.CC[NH+](CC)CC BODHJGMCSWVAGR-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PDDANVVLWYOEPS-UHFFFAOYSA-N nitrous acid;n-propan-2-ylpropan-2-amine Chemical compound [O-]N=O.CC(C)[NH2+]C(C)C PDDANVVLWYOEPS-UHFFFAOYSA-N 0.000 description 1
- YOZAGUUCIGVOFI-UHFFFAOYSA-N nitrous acid;pyridine Chemical compound [O-]N=O.C1=CC=[NH+]C=C1 YOZAGUUCIGVOFI-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 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
- 150000002978 peroxides Chemical class 0.000 description 1
- UZQDCAUYPXKVBH-UHFFFAOYSA-N phenylazanium nitrite Chemical compound ON=O.Nc1ccccc1 UZQDCAUYPXKVBH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920006312 vinyl chloride fiber Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/27—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of alkylpolyalkylene glycol esters of unsaturated carboxylic acids
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、繊維に難燃性及び防錆性を付与することができる繊維処理剤、該繊維処理剤を用いた繊維加工品の製造方法及び該繊維加工品の製造方法を用いて得られる繊維加工品に関する。
本願は、2016年4月18日に、日本に出願された特願2016-082714号に基づき優先権を主張し、その内容をここに援用する。The present invention is a fiber treatment agent capable of imparting flame retardancy and rust resistance to a fiber, a method for producing a processed fiber product using the fiber treatment agent, and a fiber obtained by using the method for producing the processed fiber product. Regarding processed products.
This application claims priority based on Japanese Patent Application No. 2016-082714 filed in Japan on April 18, 2016, the contents of which are incorporated herein by reference.
近年、建築材料や、家電、電子材料、自動車等の車両内装材等の用途において使用される繊維加工品の難燃化が求められている。また、そのような繊維加工品には、物性向上剤および接着剤として、合成樹脂及び各種添加剤を含有する繊維処理剤が広く用いられている。前記のような難燃繊維加工品を得るために、繊維に難燃性や防錆性を付与する繊維処理剤が求められている。そのような繊維処理剤の開発が進められている。 In recent years, there has been a demand for flame-retardant textile processed products used in applications such as building materials, home appliances, electronic materials, and vehicle interior materials such as automobiles. Further, in such processed fiber products, fiber treatment agents containing synthetic resins and various additives are widely used as physical property improving agents and adhesives. In order to obtain the above-mentioned flame-retardant fiber processed product, there is a demand for a fiber treatment agent that imparts flame-retardant property and rust-preventive property to the fiber. Development of such fiber treatment agents is underway.
一般的に、繊維を難燃化する方法としては、主に繊維処理剤に難燃剤を添加する方法が挙げられる。このような難燃剤として、例えば、赤リンやリン酸塩、三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウムなどの無機系難燃剤;ペンタブロモビフェニル、オクタブロモビフェニル、デカブロモビフェニルなどのハロゲン系難燃剤;リン酸グアニジン、トリフェニルホスフェート、スルファミン酸などの非ハロゲン難燃剤などが良く知られている。 In general, as a method for making a fiber flame retardant, a method of adding a flame retardant to a fiber treatment agent is mainly mentioned. Examples of such flame retardants include inorganic flame retardants such as red phosphorus, phosphate, antimony trioxide, aluminum hydroxide, and magnesium hydroxide; halogen-based flame retardants such as pentabromobiphenyl, octabromobiphenyl, and decabromobiphenyl. Flame Retardants; Non-halogen flame retardants such as guanidine phosphate, triphenyl phosphate, and sulfamic acid are well known.
しかし、これら難燃剤は、一般的に繊維処理剤中の合成樹脂との相溶性に問題があるため、繊維加工品において難燃剤成分が分離、沈降及びチョーキングを引き起こすことがある。
さらに、合成樹脂を含有する繊維処理剤においてこれらの難燃剤を用いた場合、このような繊維処理剤は、繊維加工品に難燃性を付与するだけでなく、強度や風合い、防錆性等の繊維加工品の他の諸物性に悪影響を与えないことが求められる。しかし、一般的に繊維加工品へ難燃性を付与するためには難燃剤を多量に添加する必要があるため、繊維加工品の物性を阻害する原因となっている。However, since these flame retardants generally have a problem in compatibility with the synthetic resin in the fiber treatment agent, the flame retardant component may cause separation, sedimentation and chalking in the processed fiber product.
Further, when these flame retardants are used in the fiber treatment agent containing a synthetic resin, such a fiber treatment agent not only imparts flame retardancy to the processed fiber product, but also has strength, texture, rust resistance and the like. It is required not to adversely affect other physical properties of the processed textile products of. However, in general, in order to impart flame retardancy to a processed fiber product, it is necessary to add a large amount of a flame retardant, which is a cause of impairing the physical properties of the processed fiber product.
特に無機系難燃剤は難燃化性能が乏しく、繊維処理剤への多量の添加が必要であるため、合成樹脂等の他の添加剤成分との比重差から沈降が生じやすい。また、無機系難燃剤を用いた繊維加工品では風合いが硬くなるといった問題も生じやすい。 Inorganic flame retardants in particular have poor flame retardant performance and need to be added in a large amount to the fiber treatment agent, so that precipitation is likely to occur due to the difference in specific gravity with other additive components such as synthetic resin. In addition, a fiber processed product using an inorganic flame retardant tends to have a problem that the texture becomes hard.
一方、ハロゲン系難燃剤は難燃化性能が優れているため、繊維処理剤への添加が少量で済む。このことから、これらを含む繊維処理剤を用いて加工した繊維加工品の物性に与える影響は少ない。しかし、塩素や臭素といったハロゲン元素を含有しているため、これらを用いた繊維加工品を焼却する場合にダイオキシンやハロゲン化水素といった有害な物質を発生する恐れがあり、EU諸国を始めとした世界各国で規制や使用の見直しが行われている。 On the other hand, since the halogen-based flame retardant has excellent flame retardant performance, it can be added to the fiber treatment agent in a small amount. From this, the influence on the physical characteristics of the fiber processed product processed by using the fiber treatment agent containing these is small. However, since it contains halogen elements such as chlorine and bromine, there is a risk of generating harmful substances such as dioxins and hydrogen halides when incinerating fiber processed products using these, and the world including EU countries. Regulations and usage are being reviewed in each country.
非ハロゲン系難燃剤は、ハロゲン系難燃剤と比較して、安全性に優れているため、リン系を始めとした難燃剤が多く検討されている。しかし、リン系難燃剤の難燃化性能はハロゲン系の難燃剤よりも低く、比較的多量に使用しなければならない。そのため、リン系難燃剤を含む繊維処理剤は、該繊維処理剤を用いて加工した繊維加工品の物性を低下させてしまう。例えば、水溶性のリン系難燃剤は潮解性が高く、見かけ上、樹脂を可塑化するため、これらを用いた繊維加工品の強度、風合いを低下させる原因となる。また、油溶性のリン系難燃剤も、樹脂の可塑化や繊維処理剤表面へのブリーディングにより、強度、風合いを低下させるだけでなく、該繊維処理剤を用いた繊維加工品でベタツキやチョーキングを生じさせる原因となっている。 Since non-halogen flame retardants are superior in safety to halogen flame retardants, many flame retardants such as phosphorus are being studied. However, the flame retardant performance of the phosphorus-based flame retardant is lower than that of the halogen-based flame retardant, and it must be used in a relatively large amount. Therefore, the fiber treatment agent containing a phosphorus-based flame retardant deteriorates the physical characteristics of the fiber processed product processed using the fiber treatment agent. For example, water-soluble phosphorus-based flame retardants have high deliquescent properties and apparently plasticize resins, which causes a decrease in the strength and texture of processed fiber products using them. In addition, the oil-soluble phosphorus-based flame retardant not only reduces the strength and texture by plasticizing the resin and bleeding on the surface of the fiber treatment agent, but also makes the fiber processed product using the fiber treatment agent sticky and chalking. It is the cause of the occurrence.
また、繊維に防錆性を付与する方法としては、主に繊維処理剤に防錆剤を添加する方法が挙げられる。例えば、亜硝酸塩、クロム酸塩、リン酸塩、ケイ酸塩などの無機系防錆剤;アルキルスルホン酸又はベンゼンスルホン酸のバリウム塩、バリウムせっけん、有機アミンのカルボン酸塩、安息香酸塩などの有機系防錆剤が良く知られている。 Moreover, as a method of imparting a rust preventive property to a fiber, a method of adding a rust preventive agent to a fiber treatment agent is mainly mentioned. For example, inorganic rust preventives such as nitrite, chromate, phosphate, silicate; barium salt of alkyl sulfonic acid or benzene sulfonic acid, barium soap, carboxylic acid salt of organic amine, benzoate, etc. Organic rust preventives are well known.
無機系防錆剤は、有機系防錆剤と比較して、防錆性に優れているため多くの検討がなされている。しかし、一般的に、無機系防錆剤には人体に有害な物質が含有されており、環境への影響が懸念されている。例えば、亜硝酸塩は高い防錆性を示すことが知られているが、人体への有害性が指摘されており、亜硝酸フリーの防錆剤が求められている。クロム酸塩も同様に高い防錆性を示すことが知られているが、重金属を含有しており、亜硝酸塩同様に人体への有害性や、その処理過程における排水規制などがあり、現在ではその使用が避けられている。 Inorganic rust preventives have been studied many times because they are superior in rust preventive properties as compared with organic rust preventives. However, in general, inorganic rust inhibitors contain substances harmful to the human body, and there is concern about their impact on the environment. For example, nitrite is known to exhibit high rust preventive properties, but it has been pointed out that it is harmful to the human body, and nitrite-free rust preventive agents are required. Chromate is also known to exhibit high rust resistance, but it contains heavy metals and is harmful to the human body like nitrite, and there are restrictions on wastewater in the treatment process. Its use is avoided.
有機系防錆剤は、前記無機系防錆剤で指摘されていたような人体への有害性や環境負荷といった課題を解決するものとして広く使用されている。高い防錆性を示す有機系防錆剤として、例えば、アルキルスルホン酸又はベンゼンスルホン酸のバリウム塩、バリウムせっけん等が知られているが、近年、バリウム塩の人体に対する有害性が指摘され、その使用に対する欧米等の規制が行われている。アルキルコハク酸ハーフエステル、アルケニルコハク酸ハーフエステル等の各種のカルボン酸エステルは一定の防錆性を示すが、十分なものではない。一方、安息香酸塩は防錆性を示すことが知られており、自動車エンジン用不凍冷却液の添加剤等にも用いられている。また、一般的に安息香酸塩は人体に与える影響が軽微であり、食品保存料等に用いられるなど、無機系防錆剤に比べて環境負荷が低いといった利点がある。しかしながら、一般的に有機系防錆剤は可燃性であり、これらを用いた繊維処理剤では、繊維加工品の難燃性を低下させる原因となっている。 Organic rust preventives are widely used to solve problems such as harmfulness to the human body and environmental load as pointed out by the inorganic rust preventives. As an organic rust preventive agent exhibiting high rust preventive properties, for example, barium salt of alkyl sulfonic acid or benzene sulfonic acid, barium soap and the like are known, but in recent years, the harmfulness of barium salt to the human body has been pointed out. There are restrictions on use in Europe and the United States. Various carboxylic acid esters such as alkyl succinic acid half ester and alkenyl succinic acid half ester show a certain degree of rust resistance, but are not sufficient. On the other hand, benzoate is known to exhibit rust preventive properties, and is also used as an additive for antifreeze coolant for automobile engines. In addition, benzoate generally has a slight effect on the human body, and has an advantage that it has a lower environmental load than an inorganic rust preventive, such as being used as a food preservative. However, organic rust inhibitors are generally flammable, and fiber treatment agents using them are a cause of lowering the flame retardancy of processed fiber products.
例えば、特許文献1に開示される、リン酸基や亜リン酸基骨格を有する不飽和単量体と、アクリル酸系不飽和単量体と、酢酸ビニル単量体とを共重合した非ハロゲン系の難燃性樹脂組成物が提案されているが、該難燃性樹脂組成物を用いた加工品は強度、剛軟性を満足するものではなく、さらなる物性向上が望まれていた。 For example, a non-halogen copolymerized with an unsaturated monomer having a phosphoric acid group or a phosphite group skeleton, an acrylic acid-based unsaturated monomer, and a vinyl acetate monomer disclosed in Patent Document 1. Although a flame-retardant resin composition of the system has been proposed, a processed product using the flame-retardant resin composition does not satisfy strength and rigidity, and further improvement in physical properties has been desired.
また、例えば、特許文献2には、難燃性樹脂組成物を用いた加工品が開示されたが、防錆性に関する開示がない。難燃性と防錆性を両立する加工品が得られる繊維処理剤が望まれていた。 Further, for example, Patent Document 2 discloses a processed product using a flame-retardant resin composition, but does not disclose rust prevention. There has been a demand for a fiber treatment agent capable of obtaining a processed product having both flame retardancy and rust prevention.
従って、本発明は、難燃性及び防錆性が共に優れた処理加工品が得られる、繊維処理剤を提供することにある。また、本発明の他の目的は、該繊維処理剤を用いた繊維加工品の製造方法及び該繊維加工品の製造方法を用いて得られる繊維加工品を提供することにある。 Therefore, the present invention is to provide a fiber treatment agent capable of obtaining a treated processed product having excellent flame retardancy and rust prevention. Another object of the present invention is to provide a method for producing a processed fiber product using the fiber treatment agent and a processed fiber product obtained by using the method for producing the processed fiber product.
すなわち、本発明は、以下の〔1〕~〔11〕に関する。
〔1〕リン含有不飽和単量体(A)と重合性不飽和単量体(B)との共重合体(P)と、防錆剤(C)と、難燃剤(D)と、を含む繊維処理剤であって、前記重合性不飽和単量体(B)が、(メタ)アクリル酸アルキルエステル不飽和単量体(b1)と、(メタ)アクリル酸及びイタコン酸からなる群から選択される少なくとも一種の不飽和単量体(b2)と、を含むことを特徴とする繊維処理剤。
〔2〕前記リン含有不飽和単量体(A)が、リン酸基又は亜リン酸基を有する単量体(a1)を含む、上記〔1〕に記載の繊維処理剤。
〔3〕前記リン酸基又は亜リン酸基を有する単量体(a1)が、アシッド・ホスホオキシポリオキシアルキレングリコールモノ(メタ)アクリレートを含む、上記〔2〕に記載の繊維処理剤。
〔4〕前記防錆剤(C)が、アミンのカルボン酸塩、安息香酸塩を含む、上記〔1〕~〔3〕のいずれかに記載の繊維処理剤。
〔5〕前記難燃剤(D)が、リンを含有する、上記〔1〕~〔4〕のいずれかに記載の繊維処理剤。
〔6〕前記重合性不飽和単量体(B)を、共重合体(P)中の全単量体に対し40質量%以上含有する、上記〔1〕~〔5〕のいずれかに記載の繊維処理剤。
〔7〕前記防錆剤(C)を、全繊維処理剤に対し0.1~15質量%含有する、上記〔1〕~〔6〕のいずれかに記載の繊維処理剤。
〔8〕前記難燃剤(D)を、全繊維処理剤に対し0.1~70質量%含有する、上記〔1〕~〔7〕のいずれかに記載の繊維処理剤。
〔9〕繊維処理剤中のリン原子量が0.01~30質量%である、上記〔1〕~〔8〕のいずれかに記載の繊維処理剤。
〔10〕上記〔1〕~〔9〕のいずれかに記載の繊維処理剤を用いて繊維基材を処理し、繊維加工品を得る工程を有する、繊維加工品の製造方法。
〔11〕乾燥後の上記〔1〕~〔9〕のいずれかに記載の繊維処理剤の付着量が、繊維基材100質量部に対し50~100質量部である、繊維加工品。That is, the present invention relates to the following [1] to [11].
[1] A copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B), a rust preventive agent (C), and a flame retardant agent (D). A fiber treatment agent containing, wherein the polymerizable unsaturated monomer (B) is composed of a (meth) acrylic acid alkyl ester unsaturated monomer (b1), (meth) acrylic acid and itaconic acid. A fiber treatment agent comprising at least one unsaturated monomer (b2) selected.
[2] The fiber treatment agent according to the above [1], wherein the phosphorus-containing unsaturated monomer (A) contains a monomer (a1) having a phosphoric acid group or a phosphorous acid group.
[3] The fiber treatment agent according to the above [2], wherein the monomer (a1) having a phosphoric acid group or a phosphorous acid group contains an acid phosphooxypolyoxyalkylene glycol mono (meth) acrylate.
[4] The fiber treatment agent according to any one of the above [1] to [3], wherein the rust preventive agent (C) contains an amine carboxylate and a benzoate.
[5] The fiber treatment agent according to any one of [1] to [4] above, wherein the flame retardant (D) contains phosphorus.
[6] The above-mentioned [1] to [5], wherein the polymerizable unsaturated monomer (B) is contained in an amount of 40% by mass or more based on all the monomers in the copolymer (P). Fiber treatment agent.
[7] The fiber treatment agent according to any one of the above [1] to [6], which contains the rust preventive agent (C) in an amount of 0.1 to 15% by mass with respect to the total fiber treatment agent.
[8] The fiber treatment agent according to any one of the above [1] to [7], which contains the flame retardant (D) in an amount of 0.1 to 70% by mass with respect to the total fiber treatment agent.
[9] The fiber treatment agent according to any one of the above [1] to [8], wherein the phosphorus atomic weight in the fiber treatment agent is 0.01 to 30% by mass.
[10] A method for producing a processed fiber product, which comprises a step of treating a fiber base material with the fiber treatment agent according to any one of the above [1] to [9] to obtain a processed fiber product.
[11] A processed fiber product in which the amount of the fiber treatment agent adhered to any one of the above [1] to [9] after drying is 50 to 100 parts by mass with respect to 100 parts by mass of the fiber base material.
本発明の繊維処理剤は、処理された加工品が優れた難燃性を有し、かつ防錆性が共に優れている。該繊維処理剤を用いた繊維加工品の製造方法により得られる繊維加工品は、難燃性及び防錆性に共に優れることから、家電、電子材料、自動車内装材用途の繊維用素材として好適である。 In the fiber treatment agent of the present invention, the treated processed product has excellent flame retardancy and also has excellent rust prevention properties. The fiber processed product obtained by the method for manufacturing a fiber processed product using the fiber treatment agent is excellent in both flame retardancy and rust prevention, and is therefore suitable as a fiber material for home appliances, electronic materials, and automobile interior materials. be.
以下、本発明を詳細に説明する。
[繊維処理剤]Hereinafter, the present invention will be described in detail.
[Fiber treatment agent]
本発明の繊維処理剤は、リン含有不飽和単量体(A)と、重合性不飽和単量体(B)との共重合体(P)と、防錆剤(C)及び難燃剤(D)とを含む。
本実施の形態に係る繊維処理剤は、処理された加工品について難燃性と防錆性との両方が共に優れ、繊維用の難燃処理剤として有用であり、各種繊維に好適に使用できる。
ここで、本明細書における「~」は、「~」という記載の前の値以上、「~」という記載の後の値以下を意味する。The fiber treatment agent of the present invention is a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B), a rust preventive agent (C), and a flame retardant ( D) and is included.
The fiber treatment agent according to the present embodiment is excellent in both flame retardancy and rust prevention property for the treated processed product, is useful as a flame retardant treatment agent for fibers, and can be suitably used for various fibers. ..
Here, "-" in the present specification means not more than the value before the description of "-" and less than or equal to the value after the description of "-".
また、本明細書における「(メタ)アクリレート」等の記載は、「アクリレート及び/又はメタクリレート」等と同義である。 Further, the description of "(meth) acrylate" and the like in the present specification is synonymous with "acrylate and / or methacrylate" and the like.
(共重合体(P))
本発明にかかる共重合体(P)は、リン含有不飽和単量体(A)と重合性不飽和単量体(B)とを重合させて得られる共重合体である。(Copolymer (P))
The copolymer (P) according to the present invention is a copolymer obtained by polymerizing a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B).
<リン含有不飽和単量体(A)>
本発明において用いるリン含有不飽和単量体(A)は、分子中にエチレン性不飽和結合と、リン原子と、を含有するものであれば特に制限されない。
前記リン含有不飽和単量体(A)の具体例としては、ジメチルビニルホスホナート、ジエチルビニルホスホナート、ジフェニルビニルホスホナート、ジフェニルビニルホスホナート、ジメチル(1,2-ジフェニル-エテニル)ホスホナート、ジメチル-p-ビニルベンジルホスホナート、ジエチル-p-ビニルベンジルホスホナート、ジフェニル-p-ビニルベンジルホスフィンオキシド、9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキシド-10-p-ビニルベンジル、アシッド・ホスホオキシエチル(メタ)アクリレート、2-アクリロイルオキシエチルアシッドホスフェート、ジフェニル-2-メタクリロイルオキシエチルホスフェート、(メタ)アクロイル・オキシエチルアシッドホスフェート・モノエタノールアミン塩、アシッド・ホスホオキシポリオキシエチレングリコールモノ(メタ)アクリレート及びアシッド・ホスホオキシポリオキシプロピレングリコール(メタ)アクリレート、並びこれらの金属塩、アンモニウム塩及びアミン塩等を挙げることができる。これらの化合物は、単独で又は二種以上の混合物として使用することができる。<Phosphorus-containing unsaturated monomer (A)>
The phosphorus-containing unsaturated monomer (A) used in the present invention is not particularly limited as long as it contains an ethylenically unsaturated bond and a phosphorus atom in the molecule.
Specific examples of the phosphorus-containing unsaturated monomer (A) include dimethylvinylphosphonate, diethylvinylphosphonate, diphenylvinylphosphonate, diphenylvinylphosphonate, dimethyl (1,2-diphenyl-ethenyl) phosphonate, and dimethyl. -P-vinylbenzylphosphonate, diethyl-p-vinylbenzylphosphonate, diphenyl-p-vinylbenzylphosphine oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-p- Vinylbenzyl, acid phosphooxyethyl (meth) acrylate, 2-acryloyloxyethyl acid phosphate, diphenyl-2-methacryloyloxyethyl phosphate, (meth) acryloyl oxyethyl acid phosphate monoethanolamine salt, acid phosphooxypoly Examples thereof include oxyethylene glycol mono (meth) acrylate and acid phosphooxypolyoxypropylene glycol (meth) acrylate, as well as metal salts, ammonium salts and amine salts thereof. These compounds can be used alone or as a mixture of two or more.
〔リン酸基又は亜リン酸基を有する単量体(a1)〕
前記リン含有不飽和単量体(A)としては、リン酸基又は亜リン酸基を有する単量体(a1)が好ましい。前記リン酸基又は亜リン酸基を有する単量体(a1)としては、例えば、一般式(1):
(式中、R1及びR2は、それぞれ独立して水素又は炭素数1~3のアルキル基を表し;Yは、ヒドロキシル基、炭素数1~3のアルキル基又は炭素数1~3のアルキルエステル基を表し;Zは、水素原子、ヒドロキシル基、炭素数1~3のアルキル基又は炭素数1~3のアルキルエステル基を表し;nは1~20の整数である)で示される化合物、並びこの化合物の金属塩、アンモニウム塩及びアミン塩等が挙げられる。これらの化合物は、単独で又は二種以上の混合物として使用することができる。R1、R2、Y、Zはそれぞれ、水素又はメチル基が好ましい。また、nは1~3が好ましい。[Monomer having a phosphoric acid group or a phosphorous acid group (a1)]
As the phosphorus-containing unsaturated monomer (A), a monomer (a1) having a phosphoric acid group or a phosphorous acid group is preferable. As the monomer (a1) having a phosphoric acid group or a phosphorous acid group, for example, the general formula (1):
(In the formula, R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms; Y is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or an alkyl having 1 to 3 carbon atoms. A compound represented by an ester group; Z represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or an alkyl ester group having 1 to 3 carbon atoms; n is an integer of 1 to 20). Examples thereof include metal salts, ammonium salts and amine salts of this compound. These compounds can be used alone or as a mixture of two or more. Hydrogen or a methyl group is preferable for R 1 , R 2 , Y and Z, respectively. Further, n is preferably 1 to 3.
前記リン酸基又は亜リン酸基を有する単量体(a1)の具体例としては、アシッド・ホスホオキシポリオキシアルキレングリコールモノ(メタ)アクリレートが挙げられる。より具体的には、アシッド・ホスホオキシエチル(メタ)アクリレート、2-アクリロイルオキシエチルアシッドホスフェート、2-メタクロイロキシエチルアシッドホスフェート、アシッド・ホスホオキシポリオキシエチレングリコールモノ(メタ)アクリレート及びアシッド・ホスホオキシポリオキシプロピレングリコール(メタ)アクリレート等を挙げることができる。これらの化合物は、単独で又は二種以上の混合物として使用することができる。中でも、1分子あたりのリン含有量が高い点で、アシッド・ホスホオキシエチル(メタ)アクリレートが好ましい。 Specific examples of the monomer (a1) having a phosphoric acid group or a phosphorous acid group include acid phosphooxypolyoxyalkylene glycol mono (meth) acrylate. More specifically, acid phosphooxyethyl (meth) acrylate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate and acid phospho. Oxypolyoxypropylene glycol (meth) acrylate and the like can be mentioned. These compounds can be used alone or as a mixture of two or more. Among them, acid phosphooxyethyl (meth) acrylate is preferable because the phosphorus content per molecule is high.
前記リン含有不飽和単量体(A)は、リン含有不飽和単量体(A)と重合性不飽和単量体(B)との共重合体(P)中の全単量体に対し20質量%~60質量%の範囲で使用することが好ましく、23~50質量%の範囲で使用することがより好ましく、26質量%~40質量%の範囲で使用することがさらに好ましい。20質量%以上であると本繊維処理剤で処理された加工品の難燃性が十分であり、60質量%以下であれば重合が安定し、本繊維処理剤を用いた加工品の強度や耐熱黄変性が低下することがない傾向にある。 The phosphorus-containing unsaturated monomer (A) is used with respect to all the monomers in the copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B). It is preferably used in the range of 20% by mass to 60% by mass, more preferably in the range of 23 to 50% by mass, and even more preferably in the range of 26% by mass to 40% by mass. If it is 20% by mass or more, the flame retardancy of the processed product treated with this fiber treatment agent is sufficient, and if it is 60% by mass or less, the polymerization is stable, and the strength of the processed product using this fiber treatment agent is increased. There is a tendency that heat-resistant yellowing does not decrease.
また、前記リン含有不飽和単量体(A)の重合割合は、リン含有不飽和単量体(A)と、重合性不飽和単量体(B)と共重合体(P)において、(A)成分と(B)成分中の、リンの原子量およびリン含有不飽和単量体(A)の分子量から計算されるリン原子の含有量が3~13質量%となるように適宜決定すればよい。難燃性付与と共重合体(P)の重合安定性、加工品における物性発現のバランスを考慮すると、リン含有量が3~10質量%となるように重合することが好ましい。3質量%より多ければ、共重合体(P)自身の難燃性が十分であるため繊維処理剤としての難燃性が十分であり、13質量%未満では共重合体(P)の重合が安定する。 Further, the polymerization ratio of the phosphorus-containing unsaturated monomer (A) is as follows in the phosphorus-containing unsaturated monomer (A), the polymerizable unsaturated monomer (B) and the copolymer (P). If the content of the phosphorus atom calculated from the atomic weight of phosphorus and the molecular weight of the phosphorus-containing unsaturated monomer (A) in the component A) and the component (B) is appropriately determined to be 3 to 13% by mass. good. Considering the balance between imparting flame retardancy, polymerization stability of the copolymer (P), and expression of physical properties in the processed product, it is preferable to polymerize so that the phosphorus content is 3 to 10% by mass. If it is more than 3% by mass, the flame retardancy of the copolymer (P) itself is sufficient, so that the flame retardancy as a fiber treatment agent is sufficient, and if it is less than 13% by mass, the copolymer (P) is polymerized. Stabilize.
<重合性不飽和単量体(B)>
本発明において用いる重合性不飽和単量体(B)は、分子中にエチレン性不飽和結合を有しており、重合性を発現し、前記リン含有不飽和単量体(A)と共重合するものであれば特に制限されない。また、複数の種類の単量体であってもよい。<Polymerizable unsaturated monomer (B)>
The polymerizable unsaturated monomer (B) used in the present invention has an ethylenically unsaturated bond in the molecule, exhibits polymerizable properties, and is copolymerized with the phosphorus-containing unsaturated monomer (A). There are no particular restrictions as long as it does. Further, it may be a plurality of types of monomers.
前記重合性不飽和単量体(B)としては、例えば、アクリル酸、メタクリル酸、フマル酸、マレイン酸及びそれらのエステル類;(メタ)アクリルアミド及びその誘導体;スチレン及びその誘導体;ビニルエステル;N置換マレイミド化合物;イタコン酸、クロトン酸、フタル酸及びそれらのエステル類及びそれらの金属塩、アンモニウム塩等が挙げられる。 Examples of the polymerizable unsaturated monomer (B) include acrylic acid, methacrylic acid, fumaric acid, maleic acid and their esters; (meth) acrylamide and its derivatives; styrene and its derivatives; vinyl esters; N. Substituted maleimide compounds; itaconic acid, crotonic acid, fumaric acid and their esters and their metal salts, ammonium salts and the like can be mentioned.
また、前記重合性不飽和単量体(B)の具体例としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、アリル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、メトキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレート、エチレングリコールモノ(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート、ポリテトラメチレングリコールモノ(メタ)アクリレート、ポリエチレングリコールポリテトラメチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールポリテトラメチレングリコールモノ(メタ)アクリレート、グリシジル(メタ)アクリレート、メチルグリシジル(メタ)アクリレート、3,4-エポキシシクロヘキシルメチル(メタ)アクリレート、エタンジオールジ(メタ)アクリレート、プロパンジオールジ(メタ)アクリレート、ブタンジオールジ(メタ)アクリレート、ヘキサンジオールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジメチロールトリシクロデカンジ(メタ)アクリレート、イソボロニル(メタ)アクリレート、フェノキシポリエチレングリコール(メタ)アクリレート、ペンタエリトリットテトラ(メタ)アクリレート等の(メタ)アクリル酸エステル;ジメチルフマレート、ジエチルフマレート、ジブチルフマレート、ジ-(2-エチルヘキシル)フマレート等のフマル酸エステル;ジメチルマレート、ジエチルマレート、ジブチルマレート、ジ-(2-エチルヘキシル)マレート等のマレイン酸エステル;メタクリルアミド;N-メチル(メタ)アクリルアミド、N-エチル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-プロピル(メタ)アクリルアミド等の(メタ)アクリルアミド誘導体;メトキシスチレン、エトキシスチレンビニル安息香酸、ビニル安息香酸メチル、ビニルベンジルアセテート、ヒドロキシスチレン、ジビニルベンゼン等のスチレン誘導体;酢酸ビニル;プロピオン酸ビニル、カプロン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル等のビニルエステル類;メチルマレイミド、エチルマレイミド、イソプロピルマレイミド、シクロヘキシルマレイミド、フェニルマレイミド、ベンジルマレイミド、ナフチルマレイミド等のN置換マレイミド化合物;モノメチルイタコネート、ジメチルイタコネート、モノエチルイタコネート、ジエチルイタコネート、モノブチルイタコネート、ジブチルイタコネート等のイタコン酸エステル;メチルクロトネート、エチルクロトネート、ブチルクロトネート等のクロトン酸エステル;ジメチルフタレート、ジエチルフタレート、ジプロピルフタレート、ジブチルフタレート、ジヘキシルフタレート等のフタル酸エステル;等が挙げられ、これらは単独又は二種以上を組み合わせて使用することができる。 Specific examples of the polymerizable unsaturated monomer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Allyl (meth) acrylate, ethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, ethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene Glycolpolytetramethylene glycol mono (meth) acrylate, polypropylene glycolpolytetramethylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, ethanediol Di (meth) acrylate, propanediol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethyl propantri. (Meta) acrylic acid esters such as (meth) acrylates, dimethyloltricyclodecandi (meth) acrylates, isobolonyl (meth) acrylates, phenoxypolyethylene glycol (meth) acrylates, pentaerythrittetra (meth) acrylates; dimethyl fumarate Acrylate such as dimethylmalate, diethylmalate, dibutylmalate, di-(2-ethylhexyl) malate; methacrylic Amid; (meth) acrylamide derivatives such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (meth) acrylamide; methoxystyrene, ethoxystyrene vinyl benzo Stylized derivatives such as acid, methyl vinylbenzoate, vinylbenzylacetate, hydroxystyrene, divinylbenzene; vinyl acetate; vinyl esters such as vinyl propionate, vinyl caproate, vinyl caprice, vinyl laurate, vinyl stearate; methyl N-substituted maleimide compounds such as maleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide; monomethylitaconate, dimethylitaconate, monoethylitaconate, diethylitaconate, monobutylitaconate, dibutylitaco Itaconic acid esters such as nate; crotonic acid esters such as methylcrotonate, ethylcrotonate and butylcrotonate; phthalic acid esters such as dimethylphthalate, diethylphthalate, dipropylphthalate, dibutylphthalate and dihexylphthalate; and the like. These can be used alone or in combination of two or more.
前記重合性不飽和単量体(B)の中でも、特に、本繊維処理剤で処理することにより得られる繊維加工品における難燃性発現の観点から、(メタ)アクリル酸アルキルエステル不飽和単量体(b1)及び(メタ)アクリル酸及びイタコン酸からなる群から選択される少なくとも一種の不飽和単量体(b2)を共に用いるのが好ましい。(メタ)アクリル酸アルキルエステル不飽和単量体(b1)を用いると、本発明の繊維処理剤を用いて処理した繊維加工品における難燃剤(D)成分の耐ブリーディング性が向上するという面で、好ましい。(メタ)アクリル酸及びイタコン酸からなる群から選択される少なくとも一種の不飽和単量体(b2)を用いると、本発明の繊維処理剤を用いて処理した繊維加工品の防錆性が向上するという面で、好ましい。 Among the polymerizable unsaturated monomers (B), a single amount of (meth) acrylic acid alkyl ester unsaturated, particularly from the viewpoint of exhibiting flame retardancy in a fiber processed product obtained by treating with this fiber treatment agent. It is preferable to use at least one unsaturated monomer (b2) selected from the group consisting of the body (b1) and (meth) acrylic acid and itaconic acid. When the (meth) acrylic acid alkyl ester unsaturated monomer (b1) is used, the bleeding resistance of the flame retardant (D) component in the processed fiber product treated with the fiber treatment agent of the present invention is improved. ,preferable. When at least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid is used, the rust resistance of the processed fiber product treated with the fiber treatment agent of the present invention is improved. It is preferable in terms of doing so.
〔(メタ)アクリル酸アルキルエステル不飽和単量体(b1)〕
(メタ)アクリル酸アルキルエステル不飽和単量体(b1)のアルキル基は、炭素数1~5のアルキルであることが好ましい。具体例としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレートなどが挙げられ、なかでも難燃性発現の点でメチル(メタ)アクリレート、エチル(メタ)アクリレートが好ましい。これらは単独又は二種以上を組み合わせて使用することができる。[(Meta) Acrylic Acid Alkyl Ester Unsaturated Monomer (b1)]
The alkyl group of the (meth) acrylic acid alkyl ester unsaturated monomer (b1) is preferably an alkyl having 1 to 5 carbon atoms. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and among them, methyl (meth) acrylate and ethyl (meth) acrylate in terms of flame retardancy. Meta) acrylate is preferred. These can be used alone or in combination of two or more.
また、さらに、他の(メタ)アクリル酸アルキルエステル不飽和単量体(b1)を用いてもよい。具体例としては、2-エチルヘキシル(メタ)アクリレート、アリル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、メトキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート等が挙げられ、これらは単独又は二種以上を組み合わせて使用することができる。 Further, another (meth) acrylic acid alkyl ester unsaturated monomer (b1) may be used. Specific examples include 2-ethylhexyl (meth) acrylate, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylamino. Ethyl (meth) acrylate and the like can be mentioned, and these can be used alone or in combination of two or more.
〔(メタ)アクリル酸及びイタコン酸からなる群から選択される少なくとも一種の不飽和単量体(b2)〕
(メタ)アクリル酸及びイタコン酸からなる群から選択される少なくとも一種の不飽和単量体(b2)は、本発明の繊維処理剤の難燃性を向上させるために使用する。中でも、重合の安定性を損なうことがなく、共重合体(P)中の含有量を高くすることができるという面で、アクリル酸が好ましい。
また、(メタ)アクリル酸及びイタコン酸からなる群から選択される少なくとも一種の不飽和単量体(b2)と併用して、(メタ)アクリル酸及びイタコン酸からなる群以外から選択されるカルボキシル基を有する不飽和単量体を用いてもよい。(メタ)アクリル酸及びイタコン酸からなる群以外から選択されるカルボキシル基を有する不飽和単量体の具体例としては、フマル酸、マレイン酸、クロトン酸等が挙げられ、これらは単独又は二種以上を組み合わせて使用することができる。[At least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid]
At least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid is used to improve the flame retardancy of the fiber treatment agent of the present invention. Among them, acrylic acid is preferable in that the content in the copolymer (P) can be increased without impairing the stability of the polymerization.
In addition, a carboxyl selected from a group other than the group consisting of (meth) acrylic acid and itaconic acid in combination with at least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid. Unsaturated monomers having a group may be used. Specific examples of unsaturated monomers having a carboxyl group selected from the group other than the group consisting of (meth) acrylic acid and itaconic acid include fumaric acid, maleic acid, crotonic acid and the like, and these are one or two kinds. The above can be used in combination.
前記重合性不飽和単量体(B)は、繊維処理剤に含まれる、リン含有不飽和単量体(A)と重合性不飽和単量体(B)との共重合体(P)中の全単量体に対し、その合計で40質量%以上使用することが好ましく、50質量%~80質量%使用することがより好ましい。
40質量%以上であると、本発明の繊維処理剤の重合が安定し、80質量%以下であると、本発明の繊維処理剤を用いて処理した繊維加工品の難燃性が十分である傾向にある。
重合性不飽和単量体(B)において、(メタ)アクリル酸アルキルエステル不飽和単量体(b1)及び(メタ)アクリル酸及びイタコン酸からなる群から選択される少なくとも一種の不飽和単量体(b2)の合計量は90質量%以上が好ましく、より好ましくは95質量%以上であり、さらに好ましくは100質量%である。
重合性不飽和単量体(B)において、(メタ)アクリル酸アルキルエステル不飽和単量体(b1)及び(メタ)アクリル酸及びイタコン酸からなる群から選択される少なくとも一種の不飽和単量体(b2)との質量比(b1/b2)は、例えば、96/4~4/96であることが好ましく、79/21~21/79であることがより好ましく、75/25~30/70であることが更に好ましい。その範囲内の場合、本発明の繊維処理剤を用いて処理した繊維加工品における難燃剤(D)成分の耐ブリーディング性が向上する傾向にある。また、本発明の繊維処理剤を用いて処理した繊維加工品の難燃性又は防錆性が向上する傾向にある。The polymerizable unsaturated monomer (B) is contained in a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B) contained in a fiber treatment agent. It is preferable to use 40% by mass or more in total, and more preferably 50% by mass to 80% by mass, based on all the monomers.
When it is 40% by mass or more, the polymerization of the fiber treatment agent of the present invention is stable, and when it is 80% by mass or less, the flame retardancy of the processed fiber product treated with the fiber treatment agent of the present invention is sufficient. There is a tendency.
In the polymerizable unsaturated monomer (B), at least one unsaturated single amount selected from the group consisting of (meth) acrylic acid alkyl ester unsaturated monomer (b1) and (meth) acrylic acid and itaconic acid. The total amount of the body (b2) is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 100% by mass.
In the polymerizable unsaturated monomer (B), at least one unsaturated single amount selected from the group consisting of (meth) acrylic acid alkyl ester unsaturated monomer (b1) and (meth) acrylic acid and itaconic acid. The mass ratio (b1 / b2) to the body (b2) is preferably, for example, 96/4 to 4/96, more preferably 79/21 to 21/79, and 75/25 to 30 /. It is more preferably 70. Within that range, the bleeding resistance of the flame retardant (D) component in the processed fiber product treated with the fiber treatment agent of the present invention tends to be improved. Further, the flame retardant or rust preventive property of the processed fiber product treated with the fiber treatment agent of the present invention tends to be improved.
(共重合体(P)の製造方法)
本発明の繊維処理剤に含まれる、リン含有不飽和単量体(A)と重合性不飽和単量体(B)との共重合体(P)は、懸濁重合法、乳化重合法、溶液重合法、塊状重合法などの公知の共重合方法を用いて製造することができる。また、連続式重合法でも回分式重合法でも製造することができる。(Method for producing copolymer (P))
The copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) contained in the fiber treatment agent of the present invention is a suspension polymerization method, an emulsification polymerization method, or the like. It can be produced by using a known copolymerization method such as a solution polymerization method or a massive polymerization method. Further, it can be produced by either a continuous polymerization method or a batch polymerization method.
(防錆剤(C))
本発明において用いられる防錆剤(C)は、本発明の繊維処理剤で処理された加工品の難燃性を著しく損なわないでものであれば特に制限されない。(Rust inhibitor (C))
The rust preventive agent (C) used in the present invention is not particularly limited as long as it does not significantly impair the flame retardancy of the processed product treated with the fiber treatment agent of the present invention.
前記防錆剤(C)の具体例としては、モノ及びジイソプロピルアミンナイトライト、モノおよびジシクロヘキシルアミンナイトライト、トリエチルアミンナイトライト、ピリジンナイトライト、アニリンナイトライト等の亜硝酸塩;アルキルコハク酸ハーフエステル、アルケニルコハク酸ハーフエステル等の各種のカルボン酸エステル;ジシクロヘキシルアンモニウムサリシレート、ジシクロヘキシルアンモニウムシクロヘキサンカルボキシレート、シクロヘキシルアミンシクロヘキサンカルボキシレート、ジシクロヘキシルアンモニウムアクリレート、シクロヘキシルアミンアクリレート及びそれらのカルバミン酸塩、ナフテン酸塩、オクチル酸塩等のアミンのカルボン酸塩;エチルモルホリン安息香酸塩、ジ及びモノシクロヘキシルアミン安息香酸塩、モノエタノールアミン安息香酸塩、安息香酸ナトリウム等の安息香酸塩;各種のクロム酸塩;リン酸塩;ケイ酸塩;スルホン酸塩等が挙げられ、なかでも、環境負荷、使用規制や効率的な防錆性発現の点で、アミンのカルボン酸塩又は安息香酸塩が好ましい。これらの化合物は単独又は二種以上を組み合わせて使用することができる。 Specific examples of the rust preventive agent (C) include nitrites such as mono and diisopropylamine nitrite, mono and dicyclohexylamine nitrite, triethylamine nitrite, pyridine nitrite, and aniline nitrite; alkyl succinic acid half ester and alkenyl. Various carboxylic acid esters such as succinic acid half ester; dicyclohexylammonium salicylate, dicyclohexylammonium cyclohexanecarboxylate, cyclohexylaminecyclohexanecarboxylate, dicyclohexylammonium acrylate, cyclohexylamine acrylate and their carbamates, naphthenates, octylates, etc. Amine carboxylates; ethylmorpholine benzoates, di and monocyclohexylamine benzoates, monoethanolamine benzoates, benzoates such as sodium benzoate; various chromates; phosphates; silicic acid. Salts; sulfonates and the like can be mentioned, and among them, amine carboxylates or benzoates are preferable in terms of environmental load, usage regulation and efficient rust-preventive development. These compounds may be used alone or in combination of two or more.
本発明の繊維処理剤における、防錆剤(C)の含有量は、0.1~15質量%が好ましく、0.5~10質量%であることがより好ましく、1~5質量%であることが更に好ましい。0.1質量%より少なくなると、本発明の繊維処理剤に処理された加工品の防錆性が低下し、15質量%より多くなると、繊維処理剤の乾燥性が低下し、該繊維処理剤を処理することで得られる繊維加工品の物性を阻害したり、該繊維加工品の処理性が低下する傾向にある。また、この範囲になると、本発明の繊維処理剤に用いて処理された加工品の防錆性が低下することなく、下記の適量な難燃剤との併用によって、加工品の難燃性も低下することがない。 The content of the rust preventive agent (C) in the fiber treatment agent of the present invention is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and 1 to 5% by mass. Is even more preferable. When it is less than 0.1% by mass, the rust resistance of the processed product treated with the fiber treatment agent of the present invention is lowered, and when it is more than 15% by mass, the drying property of the fiber treatment agent is lowered, and the fiber treatment agent is said. There is a tendency that the physical properties of the processed fiber product obtained by the treatment are impaired or the processability of the processed fiber product is lowered. Further, within this range, the rust preventive property of the processed product treated with the fiber treatment agent of the present invention does not decrease, and the flame retardancy of the processed product also decreases when used in combination with the following appropriate flame retardant. There is nothing to do.
(難燃剤(D))
本発明において用いられる難燃剤(D)は、繊維処理剤中に混合できるものであれば特に制限されない。(Flame retardant (D))
The flame retardant (D) used in the present invention is not particularly limited as long as it can be mixed in the fiber treatment agent.
前記難燃剤(D)の具体例としては、グアニジンホスフェート、トリフェニルホスフェート、クレジルジフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリス(t-ブチル化フェニル)ホスフェート、トリス(i-プロピル化フェニル)ホスフェート、2-エチルヘキシルジフェニルホスフェート、赤リン、1,3-フェニレンビス(ジフェニルホスフェート)、1,3-フェニレンビス(ジキシレニルホスフェート)、ビスフェノールAビス(ジフェニルホスフェート)及びそれらの金属塩等のリン系難燃剤;三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、アンチモンソーダ、水酸化アルミニウム、水酸化マグネシウム等の無機系難燃剤;メラミンシアヌレート等の窒素系難燃剤;ペンタブロモビフェニル、オクタブロモビフェニル、デカブロモビフェニル等のハロゲン系難燃剤等が挙げられる。なかでも、環境負荷の低さや効率的な難燃性発現の点で、リンを含有する難燃剤を用いることが好ましい。これらの化合物は単独又は二種以上を組み合わせて使用することができる。 Specific examples of the flame retardant (D) include guanidine phosphate, triphenyl phosphate, cresyldiphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (t-butylated phenyl) phosphate, and tris (i-propylated). Phenyl) phosphate, 2-ethylhexyl diphenyl phosphate, red phosphorus, 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate) and their metal salts, etc. Phosphorus flame retardants; Antimonite trioxide, Antimon tetroxide, Antimon pentoxide, Antimon soda, Aluminum hydroxide, Inorganic flame retardants such as magnesium hydroxide; Nitrogen flame retardants such as melamine cyanurate; Pentabromobiphenyl, Octa Examples thereof include halogen-based flame retardants such as bromobiphenyl and decabromobiphenyl. Above all, it is preferable to use a flame retardant containing phosphorus in terms of low environmental load and efficient flame retardant development. These compounds may be used alone or in combination of two or more.
本発明の繊維処理剤における、難燃剤(D)の含有量は、0.1~70質量%が好ましく、0.5~50質量%であることがより好ましく、1~30質量%であることが更に好ましい。0.1質量%以上であると、本発明の繊維処理剤で処理された加工品の難燃性が十分となり、70質量%以下であると、本発明の繊維処理剤を用いて処理することで得られる繊維加工品においてチョーキングやべたつき等が抑制される傾向にある。
本発明の繊維処理剤における、難燃剤(D)の含有量は、防錆剤(C)の含有量との合計が40質量%以下であることが好ましい。40質量%以下であると、ブリーディングが抑制される傾向にあり、また、本発明の繊維処理剤を用いて処理することで得られる繊維加工品においてチョーキングやべたつき等が抑制される傾向にある。The content of the flame retardant (D) in the fiber treatment agent of the present invention is preferably 0.1 to 70% by mass, more preferably 0.5 to 50% by mass, and 1 to 30% by mass. Is more preferable. When it is 0.1% by mass or more, the flame retardancy of the processed product treated with the fiber treatment agent of the present invention becomes sufficient, and when it is 70% by mass or less, it is treated with the fiber treatment agent of the present invention. Chalking, stickiness, etc. tend to be suppressed in the processed fiber products obtained in the above.
The content of the flame retardant (D) in the fiber treatment agent of the present invention is preferably 40% by mass or less in total with the content of the rust preventive agent (C). When it is 40% by mass or less, bleeding tends to be suppressed, and chalking, stickiness and the like tend to be suppressed in the processed fiber product obtained by treatment with the fiber treatment agent of the present invention.
本発明の繊維処理剤中の合計リン原子の含有量は、0.01~30質量%が好ましく、0.05~25質量%であることがより好ましく、0.1~20質量%であることが更に好ましい。0.01質量%以上であると、本発明の繊維処理剤で処理された加工品の難燃性が十分であり、30質量%以下であると、本発明の繊維処理剤を用いて処理することで得られる繊維加工品においてチョーキングやべたつき等が抑制される傾向にある。 The total phosphorus atom content in the fiber treatment agent of the present invention is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and 0.1 to 20% by mass. Is more preferable. When it is 0.01% by mass or more, the flame retardancy of the processed product treated with the fiber treatment agent of the present invention is sufficient, and when it is 30% by mass or less, it is treated with the fiber treatment agent of the present invention. Chalking, stickiness, etc. tend to be suppressed in the resulting fiber processed products.
<その他成分>
〔開始剤〕
ラジカル重合によって、リン含有不飽和単量体(A)と、重合性不飽和単量体(B)との共重合体(P)を得る場合、重合は開始剤の存在下にて行われる。この重合反応で使用するラジカル重合開始剤はラジカル重合を開始できるものであれば特に限定されるものではなく、通常用いられている過酸化物やアゾ化合物を使用することができる。例えば、その具体例としては、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム、過酸化水素、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ジイソプロピルパーオキサイド、ジ-t-ブチルパーオキサイド、t-ブチルパーオキシベンゾエート、t-ヘキシルパーオキシベンゾエート、t-ブチルパーオキシ-2-エチルヘキサノエート、t-ヘキシルパーオキシ-2-エチルヘキサノエート、1,1-ビス(t-ブチルパーオキシ)-3,3,5-トリメチルシクロヘキサン、2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキシル-3,3-イソプロピルヒドロパーオキサイド、t-ブチルヒドロパーオキサイド、ジクミルヒドロパーオキサイド、アセチルパーオキサイド、ビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、イソブチルパーオキサイド、3,3,5-トリメチルヘキサノイルパーオキサイド、ラウリルパーオキサイド、1,1-ビス(t-ヘキシルパーオキシ)-3,3,5-トリメチルシクロヘキサン、アゾビスイソブチロニトリル、アゾビスカルボンアミド等を挙げることができ、反応によっては適当な還元剤を使用してもよい。開始剤の使用量は、共重合体(P)中の、リン含有不飽和単量体(A)及び重合性不飽和単量体(B)の合計100質量部に対して0.01~20質量部が好ましく、0.1~10質量部が更に好ましい。<Other ingredients>
[Initiator]
When a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B) is obtained by radical polymerization, the polymerization is carried out in the presence of an initiator. The radical polymerization initiator used in this polymerization reaction is not particularly limited as long as it can initiate radical polymerization, and commonly used peroxides and azo compounds can be used. For example, specific examples thereof include sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, and t-butyl peroxybenzoate. , T-Hexylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3 , 5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyl-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumylhydroperoxide, acetylper Oxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t- Hexylperoxy) -3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobiscarboxylicamide and the like can be mentioned, and an appropriate reducing agent may be used depending on the reaction. The amount of the initiator used is 0.01 to 20 with respect to 100 parts by mass of the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) in the copolymer (P). The mass is preferable, and 0.1 to 10 parts by mass is more preferable.
〔界面活性剤〕
本発明の繊維処理剤に含まれる、リン含有不飽和単量体(A)と重合性不飽和単量体(B)との共重合体(P)を、乳化重合法により製造する際には、界面活性剤の存在下で行われる。界面活性剤としては、一般に市販されているアニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤及び共重合性界面活性剤が使用できる。また、これらの界面活性剤は、単独または二種類以上を組み合わせて使用することができる。使用する界面活性剤量はリン含有不飽和単量体(A)及び重合性不飽和単量体(B)の合計に対して0.01~30質量部が好ましく、0.1~20質量部が更に好ましい。なお重合安定性の観点から、同様に水溶性(メタ)アクリル酸樹脂、水溶性(メタ)アクリル酸エステル樹脂、ポリオキシエチレンアルキルエーテル等の水溶性高分子を保護コロイドとして用いてもよい。また、これらの保護コロイドは、鹸化度、平均重合度、変性の有無に関係なく使用することができるが、平均重合度は、重合安定性、製品粘度の観点から200~2,400であることが好ましく、鹸化度は、重合安定性の観点から、80%~100%であることが好ましい。また、これらの保護コロイドの使用量は、特に制限されるものではないが、重合安定性の観点から、リン含有不飽和単量体(A)及び重合性不飽和単量体(B)の合計100質量部に対して、1~100質量部であることが好ましく、10~30質量部であることが更に好ましい。[Surfactant]
When the copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) contained in the fiber treatment agent of the present invention is produced by the emulsification polymerization method. , In the presence of a surfactant. As the surfactant, commercially available anionic surfactants, nonionic surfactants, cationic surfactants and copolymerizable surfactants can be used. In addition, these surfactants can be used alone or in combination of two or more. The amount of the surfactant used is preferably 0.01 to 30 parts by mass, preferably 0.1 to 20 parts by mass with respect to the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B). Is more preferable. Similarly, from the viewpoint of polymerization stability, a water-soluble polymer such as a water-soluble (meth) acrylic acid resin, a water-soluble (meth) acrylic acid ester resin, or a polyoxyethylene alkyl ether may be used as a protective colloid. Further, these protective colloids can be used regardless of the degree of saponification, the average degree of polymerization, and the presence or absence of modification, but the average degree of polymerization is 200 to 2,400 from the viewpoint of polymerization stability and product viscosity. The degree of saponification is preferably 80% to 100% from the viewpoint of polymerization stability. The amount of these protective colloids used is not particularly limited, but is the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) from the viewpoint of polymerization stability. It is preferably 1 to 100 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass.
〔その他の添加剤〕
本発明の繊維処理剤には、本発明の効果を損なわない範囲で、充填剤、防腐剤、着色剤、消泡剤、発泡剤、分散剤、乳化剤、流動性調整剤、可塑剤、pH調整剤、各種油剤等の添加剤を配合してもよい。[Other additives]
The fiber treatment agent of the present invention includes fillers, preservatives, colorants, defoamers, foaming agents, dispersants, emulsifiers, fluidity regulators, plasticizers, and pH adjusters as long as the effects of the present invention are not impaired. Additives such as agents and various oils may be blended.
〔その他の添加樹脂〕
また、本発明の繊維処理剤には、本発明の効果を損なわない範囲で、他の樹脂エマルジョンや溶液樹脂、エポキシ樹脂、ウレタン樹脂等の各種樹脂組成物をバインダーとして含有していてもよい。[Other additive resins]
Further, the fiber treatment agent of the present invention may contain various resin compositions such as other resin emulsions, solution resins, epoxy resins and urethane resins as binders as long as the effects of the present invention are not impaired.
〔溶媒〕
本発明の繊維処理剤の製造に用いられる溶媒は水や通常用いられている有機溶剤を使用することができる。例えばその具体例としては、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等のアルコール類;酢酸エチル、酢酸イソプロピル、セロソルブアセテート、ブチルセロソルブアセテート等のエチレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールモノメチルエーテルアセテート、カルビトールアセテート、ブチルカルビトールアセテート等のジエチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテルアセテート類等の酢酸エステル類;エチレングリコールジアルキルエーテル類、メチルカルビトール、エチルカルビトール、ブチルカルビトール等のジエチレングリコールジアルキルエーテル類、トリエチレングリコールジアルキルエーテル類、プロピレングリコールジアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、メチルエーテル、エチルエーテル、1,4-ジオキサン、テトラヒドロフラン等のエーテル類;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類;ベンゼン、トルエン、キシレン、ヘキサン、オクタン、デカン等の炭化水素類;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤;乳酸メチル、乳酸エチル、乳酸ブチル等の乳酸エステル類;ジメチルホルムアミド;N-メチルピロリドン等が挙げられる。これらの水、有機溶剤は単独又は二種以上を組み合わせて使用することができる。〔solvent〕
As the solvent used for producing the fiber treatment agent of the present invention, water or a commonly used organic solvent can be used. For example, specific examples thereof include alcohols such as methanol, ethanol, propanol, isopropanol and butanol; ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate, diethylene glycol monomethyl ether acetate and carbitol acetate. , Diethylene glycol monoalkyl ether acetates such as butyl carbitol acetate, acetate esters such as propylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers, methyl carbitol, ethyl carbitol, Diethylene glycol dialkyl ethers such as butyl carbitol, triethylene glycol dialkyl ethers, propylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, methyl ethers, ethyl ethers, 1,4-dioxane, ethers such as tetrahydrofuran; acetone, Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; hydrocarbons such as benzene, toluene, xylene, hexane, octane, decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; methyl lactate , Lactic acid esters such as ethyl lactate and butyl lactate; dimethylformamide; N-methylpyrrolidone and the like. These waters and organic solvents can be used alone or in combination of two or more.
[繊維]
本明細書において、繊維とは、各種繊維及びそれらの混紡品からなる不織布、織物、編物等を含む。また、該繊維としては、例えば、木綿、麻、絹、羊毛、コラーゲン繊維、アクリル繊維、セルロース系繊維、ポリイミド繊維、ポリアミドイミド繊維、レーヨン繊維、ナイロン繊維、ビニロン繊維、ポリエステル繊維、ポリプロピレン繊維、ポリ塩化ビニル繊維、ポリエチレン繊維、ポリメタフェニレンイソフタルアミド繊維、アラミド繊維、ポリアリレート繊維、ポリテトラフルオロエチレン繊維、ポリベンゾイミダゾール繊維、ポリエーテルエーテルケトン繊維、ポリフェニレンサルファイド繊維及びこれらの混紡品からなる不織布、織物、編物等が挙げられる。[fiber]
In the present specification, the fiber includes a non-woven fabric, a woven fabric, a knitted fabric, etc. made of various fibers and blended products thereof. The fibers include, for example, cotton, linen, silk, wool, collagen fiber, acrylic fiber, cellulose fiber, polyimide fiber, polyamideimide fiber, rayon fiber, nylon fiber, vinylon fiber, polyester fiber, polypropylene fiber, poly. Non-woven fabric consisting of vinyl chloride fiber, polyethylene fiber, polymethaphenylene isophthalamide fiber, aramid fiber, polyallylate fiber, polytetrafluoroethylene fiber, polybenzoimidazole fiber, polyether ether ketone fiber, polyphenylene sulfide fiber and a blended product thereof. Examples include textiles and knitted fabrics.
[繊維加工品の製造方法]
本発明の繊維処理剤で繊維(基材)を処理し、繊維加工品を製造する方法としては、各種公知の方法を特に制限なく採用することができる。例えば、本発明の繊維処理剤を繊維に塗布し処理する方法としては、ダイレクトコート法、スプレーコート法、ロールコーター法、スロットコーター法、ナイフコート法、プリント法、ロール転写法、等が挙げられる。また、例えば、繊維を本発明の繊維処理剤に浸漬し処理する方法としては、水平ローラー法、メタリングローラー法、スクリーンコンベア法、フォーム法、等が挙げられる。
例えば、不織布といった繊維を本発明の繊維処理剤で処理する場合の加工方法は、スプレーコート法、プリント法、ロール転写法、水平ローラー法、メタリングローラー法、スクリーンコンベア法、フォーム法、等が挙げられる。また、例えば、織物といった繊維を本発明の繊維処理剤で処理する場合の加工方法は、ダイレクトコート法、スプレーコート法、ロールコーター法、スロットコーター法、ナイフコート法、等が挙げられる。また、繊維をシート状に形成させウェブを作成し、そのウェブをさらに接着あるいは絡み合わせて布形化する場合、前記繊維処理は、ウェブ化する前の繊維に対して行っても良いし、繊維を各種の方法でウェブ化した後に行ってもよい。前記繊維ウェブ化方法は、各種公知の方法を特に制限なく採用することができ、例えば、エアレイ法等が挙げられる。[Manufacturing method of processed textile products]
As a method for producing a processed fiber product by treating the fiber (base material) with the fiber treatment agent of the present invention, various known methods can be adopted without particular limitation. For example, as a method of applying the fiber treatment agent of the present invention to a fiber and treating it, a direct coat method, a spray coat method, a roll coater method, a slot coater method, a knife coat method, a printing method, a roll transfer method and the like can be mentioned. .. Further, for example, as a method of immersing the fiber in the fiber treatment agent of the present invention for treatment, a horizontal roller method, a metering roller method, a screen conveyor method, a foam method and the like can be mentioned.
For example, when a fiber such as a non-woven fabric is treated with the fiber treatment agent of the present invention, the processing method includes a spray coating method, a printing method, a roll transfer method, a horizontal roller method, a metering roller method, a screen conveyor method, a foam method, and the like. Can be mentioned. Further, for example, when a fiber such as a woven fabric is treated with the fiber treatment agent of the present invention, a direct coat method, a spray coat method, a roll coater method, a slot coater method, a knife coat method and the like can be mentioned. Further, when the fibers are formed into a sheet to form a web, and the web is further adhered or entangled to form a cloth, the fiber treatment may be performed on the fibers before the web formation, or the fibers may be treated. May be performed after the web is created by various methods. As the fiber web forming method, various known methods can be adopted without particular limitation, and examples thereof include an air array method.
各種繊維基材に対する繊維処理剤の使用量は、基材自身の難燃性にもよるが、樹脂付着量(付着した繊維処理剤を乾燥した後の付着量)が10~200質量部/100質量部となる量が好ましく、30~150質量部/100質量部となる量がより好ましく、50~100質量部/100質量部となる量が更に好ましい。10質量部/100質量部以上であると、本発明の繊維処理剤を用いて得られる繊維加工品の難燃性及び防錆性が十分であり、200質量部/100質量部より多くなると、本発明の繊維処理剤を用いて得られる繊維加工品の強度、風合いの低下が抑制される傾向にある。乾燥は送風乾燥でもよいし、減圧乾燥でもよいし、加圧乾燥でもよい。また、加熱してもよい。乾燥の際に加熱する場合、温度は乾燥の際に加熱する場合の温度の範囲は、50~250℃が好ましく、80~190℃がより好ましい。加熱温度が低すぎると乾燥に時間がかかったり、乾燥が不充分になる可能性がある。加熱温度が高すぎると、変質を起こす可能性がある。 The amount of the fiber treatment agent used for various fiber base materials depends on the flame retardancy of the base material itself, but the amount of resin adhesion (the amount of adhesion after drying the adhered fiber treatment agent) is 10 to 200 parts by mass / 100. The amount to be parts by mass is preferable, the amount to be 30 to 150 parts by mass / 100 parts by mass is more preferable, and the amount to be 50 to 100 parts by mass / 100 parts by mass is further preferable. When it is 10 parts by mass / 100 parts by mass or more, the flame retardancy and rust resistance of the processed fiber product obtained by using the fiber treatment agent of the present invention are sufficient, and when it is more than 200 parts by mass / 100 parts by mass, it is said. The decrease in strength and texture of the processed fiber product obtained by using the fiber treatment agent of the present invention tends to be suppressed. The drying may be blast drying, vacuum drying, or pressure drying. It may also be heated. When heating during drying, the temperature range of the temperature when heating during drying is preferably 50 to 250 ° C, more preferably 80 to 190 ° C. If the heating temperature is too low, it may take a long time to dry or the drying may be insufficient. If the heating temperature is too high, it may cause deterioration.
[繊維加工品]
本発明の繊維加工品は、本発明の繊維加工品の製造方法を用いて得られる。樹脂付着量(乾燥後の繊維処理剤の付着量)が、繊維(基材)に対し50~100質量部/100質量部である10~200質量部/100質量部となる量が好ましく、30~150質量部/100質量部となる量がより好ましく、50~100質量部/100質量部となる量が更に好ましい。10質量部/100質量部以上であると、本発明の繊維加工品の難燃性及び防錆性が十分であり、200質量部/100質量部以下であると、本発明の繊維加工品の強度、風合いの低下が抑制される傾向にある。
本発明の繊維加工品は、両立する優れた難燃性と防錆性を有すること等を活かして種々の分野に適用できる。例えば、本発明の繊維加工品は、電子材料用緩衝材、家電用緩衝材、自動車内装緩衝材等として好適に用いられる。[Processed textile products]
The processed fiber product of the present invention can be obtained by using the method for producing a processed fiber product of the present invention. The amount of resin adhered (the amount of adhering fiber treatment agent after drying) is preferably 10 to 200 parts by mass / 100 parts by mass, which is 50 to 100 parts by mass / 100 parts by mass with respect to the fiber (base material). An amount of up to 150 parts by mass / 100 parts by mass is more preferable, and an amount of 50 to 100 parts by mass / 100 parts by mass is further preferable. When it is 10 parts by mass / 100 parts by mass or more, the flame retardancy and rust resistance of the processed fiber product of the present invention are sufficient, and when it is 200 parts by mass / 100 parts by mass or less, the processed fiber product of the present invention is used. The decrease in strength and texture tends to be suppressed.
The processed fiber product of the present invention can be applied to various fields by taking advantage of its excellent flame retardancy and rust resistance. For example, the processed fiber product of the present invention is suitably used as a cushioning material for electronic materials, a cushioning material for home appliances, a cushioning material for automobile interiors, and the like.
以下、実施例及び比較例を用いて本発明を更に説明するが、本発明は実施例及び比較例に限定されるものではない。 Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited to Examples and Comparative Examples.
(実施例1)
イオン交換水150gを1Lの五つ口セパラブルフラスコに入れ、撹拌しながら80℃まで加熱した。アシッドホスホオキシポリオキシエチレングリコールモノメタクリレート(共栄社化学株式会社製、ライトエステルP-1M、リン含有量15質量%)60g、メチルメタクリレート36g、エチルアクリレート36g、アクリル酸18g、ドデシルベンゼンスルホン酸ソーダ1.5g、ポリオキシエチレンアルキルエーテル7.5g、イオン交換水150gを均一に乳化した。セパラブルフラスコに過硫酸カリウム0.2gを添加し、単量体乳化物の滴下を開始することで反応を開始した。単量体乳化物は4時間掛けてセパラブルフラスコ内に添加、同時に3%過流酸カリウム水溶液30gも4時間掛けて添加した。単量体乳化物の添加終了後、80℃で2時間撹拌し、反応を終了した。セパラブルフラスコ内を冷却し、30%水酸化ナトリウム水溶液を8g添加し、系内を中和した。(Example 1)
150 g of ion-exchanged water was placed in a 1 L five-necked separable flask and heated to 80 ° C. with stirring. Acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M, phosphorus content 15% by mass) 60 g, methyl methacrylate 36 g, ethyl acrylate 36 g, acrylic acid 18 g, dodecylbenzene sulfonic acid soda 1. 5 g, 7.5 g of polyoxyethylene alkyl ether, and 150 g of ion-exchanged water were uniformly emulsified. The reaction was started by adding 0.2 g of potassium persulfate to the separable flask and starting dropping the monomeric emulsion. The monomeric emulsion was added into the separable flask over 4 hours, and at the same time, 30 g of a 3% potassium persulfate aqueous solution was also added over 4 hours. After the addition of the monomeric emulsion was completed, the mixture was stirred at 80 ° C. for 2 hours to complete the reaction. The inside of the separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the inside of the system.
その後、撹拌しながら、イオン交換水20gで希釈した難燃剤ポリリン酸アンモニウム(株式会社鈴裕製、FCP-770、リン含有量24%)20g、イオン交換水10gで希釈した防錆剤カルボキシベンゾトリアゾール(城北化学工業株式会社製、CBT-1)10gを添加し、イオン交換水10gを加えた。難燃剤と防錆剤の添加終了後、1時間撹拌し、繊維処理剤1を調製した。その組成を表1に示す。
得られた繊維処理剤1を用いて、後述の方法で繊維加工品を作製した。得られた繊維加工品の物性評価を後述の評価方法で行った。その評価結果を表4に示す。 Then, while stirring, the flame retardant ammonium polyphosphate (FCP-770, manufactured by Suzuhiro Co., Ltd., phosphorus content 24%) diluted with 20 g of ion-exchanged water and the rust preventive agent carboxybenzotriazole diluted with 10 g of ion-exchanged water. (CBT-1, manufactured by Johoku Chemical Industry Co., Ltd.) 10 g was added, and 10 g of ion-exchanged water was added. After the addition of the flame retardant and the rust preventive was completed, the mixture was stirred for 1 hour to prepare the fiber treatment agent 1. The composition is shown in Table 1.
Using the obtained fiber treatment agent 1, a processed fiber product was produced by the method described later. The physical characteristics of the obtained processed fiber product were evaluated by the evaluation method described later. The evaluation results are shown in Table 4.
(実施例2~12)
表1と表2に示す組成としたこと以外は実施例1と同様の方法で調製を行い、繊維処理剤2~12を調製した。
なお、表1と表2中における各成分の詳細は、次の通りである。
・ジフェニル-2-メタクリロイルオキシエチルホスフェート:大八化学工業株式会社製、MR-260、リン含有量8%
・1-[N,N-ビス(2-エチルヘキシル)アミノメチル]ベンゾトリアゾール:城北化学工業株式会社製、BT-LX
・トリフェニルホスフェート:大八化学工業株式会社製、TPP、リン含有量10%
・ポリビニルアルコール:株式会社クラレ製、PVA205(鹸化度86.5~89.0%、平均重合度500)
得られた繊維処理剤2~12を用いて、後述の方法で繊維加工品を作製した。得られた繊維加工品の物性評価を後述の評価方法で行った。その評価結果を表4に示す。(Examples 2 to 12)
Preparations were carried out in the same manner as in Example 1 except that the compositions shown in Tables 1 and 2 were used to prepare fiber treatment agents 2 to 12.
The details of each component in Tables 1 and 2 are as follows.
-Diphenyl-2-methacryloyloxyethyl phosphate: manufactured by Daihachi Chemical Industry Co., Ltd., MR-260, phosphorus content 8%
1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole: manufactured by Johoku Chemical Industry Co., Ltd., BT-LX
-Triphenylphosphine: manufactured by Daihachi Chemical Industry Co., Ltd., TPP, phosphorus content 10%
Polyvinyl alcohol: manufactured by Kuraray Co., Ltd., PVA205 (saponification degree 86.5 to 89.0%, average polymerization degree 500)
Using the obtained fiber treatment agents 2 to 12, processed fiber products were produced by the method described later. The physical characteristics of the obtained processed fiber product were evaluated by the evaluation method described later. The evaluation results are shown in Table 4.
(比較例1~6)
表3に示す組成としたこと以外は実施例1と同様の方法で調製を行い、繊維処理剤13~18を調製した。
得られた繊維処理剤13~18を用いて、後述の方法で繊維加工品を作製した。得られた繊維加工品の物性評価を後述の評価方法で行った。その評価結果を表5に示す。(Comparative Examples 1 to 6)
Preparations were carried out in the same manner as in Example 1 except that the compositions shown in Table 3 were used to prepare fiber treatment agents 13 to 18.
Using the obtained fiber treatment agents 13 to 18, a processed fiber product was produced by the method described later. The physical characteristics of the obtained processed fiber product were evaluated by the evaluation method described later. The evaluation results are shown in Table 5.
(繊維加工品の作製及び評価方法)
実施例1~12及び比較例1~6で得られた繊維処理剤を用いて、繊維加工品を作製した。得られた繊維加工品の物性評価を行った。繊維加工品の作製及び評価は下記の方法に従って行った。(Manufacturing and evaluation method of processed fiber products)
A processed fiber product was produced using the fiber treatment agents obtained in Examples 1 to 12 and Comparative Examples 1 to 6. The physical characteristics of the obtained processed fiber products were evaluated. The processed fiber product was prepared and evaluated according to the following method.
<基材>
本発明の実施例、比較例における繊維基材は次の通りとした。
(1)繊維
ポリエステル-セルロース不織布
(2)目付 35g/m2
(3)厚さ 200μm<Base material>
The fiber base materials in the examples and comparative examples of the present invention are as follows.
(1) Fiber Polyester-Cellulose non-woven fabric (2) Metsuke 35 g / m 2
(3) Thickness 200 μm
<加工品の作製>
実施例1~12及び比較例1~6で得られた繊維処理剤を、それぞれ、イオン交換水を用いて、固形分が15質量%となるように希釈した後、基材繊維を繊維処理剤に含浸させた。その後、繊維処理剤を含浸させた基材繊維を2本マングルで絞り、熱風式乾燥機にて130℃で10分間乾燥させた。繊維処理剤の付着量は、繊維重量に対して40~50質量%であった。
<固形分の評価方法>
所定量の試料を予め精秤してある清浄なアルミ皿(高さ約17mm、口径約40mm)にとり、感度0.5mg以下の直示天秤を用いて精秤後、内温105℃±2℃に調整した乾燥機内に1時間放置する。乾燥後の試料はデシケーター内で室温まで冷却したのち、同一直示天秤にて精秤し、次式にて固形分を算出する。
固形分(%)=乾燥後の試料重量(g)/原試料重量(g)×100
<リン原子の含有量の評価方法>
比色定量法、ICP発光分析等、どのような方法を用いてもよいが、例えば、元素分析によりリン原子の含有量を求めることができる。<Manufacturing of processed products>
The fiber treatment agents obtained in Examples 1 to 12 and Comparative Examples 1 to 6 were diluted with ion-exchanged water so that the solid content was 15% by mass, and then the base fiber was used as the fiber treatment agent. Impregnated into. Then, the base fiber impregnated with the fiber treatment agent was squeezed with two mangles and dried at 130 ° C. for 10 minutes in a hot air dryer. The amount of the fiber treatment agent attached was 40 to 50% by mass with respect to the weight of the fiber.
<Evaluation method of solid content>
A predetermined amount of sample is placed in a clean aluminum dish (height: about 17 mm, diameter: about 40 mm) that has been precisely weighed in advance, and after precision weighing using a direct balance with a sensitivity of 0.5 mg or less, the internal temperature is 105 ° C ± 2 ° C. Leave it in the dryer adjusted to 1 hour. The dried sample is cooled to room temperature in a desiccator, then precisely weighed on the same direct balance, and the solid content is calculated by the following formula.
Solid content (%) = sample weight after drying (g) / original sample weight (g) x 100
<Evaluation method of phosphorus atom content>
Any method such as a colorimetric method or ICP emission analysis may be used, and for example, the phosphorus atom content can be determined by elemental analysis.
<繊維加工品の評価>
繊維加工品の燃焼性、防錆性、ブリーディングについて評価した。<Evaluation of processed textile products>
The combustibility, rust prevention, and bleeding of processed fiber products were evaluated.
(1)難燃性
繊維加工品作製後、23℃、50%RHの条件下に12時間以上静置した試験体で、UL-94垂直燃焼試験(V-0、V-1、V-2規格)に基づき、燃焼試験を行った。試験片のサイズは、長さ127mm、幅12.7mmとした。試験片5本について、接炎を各2回、合計10回行い、消炎時間の平均秒数及び最大秒数を測定し、判定を行った。
UL-94 垂直燃焼性試験(V)
V-0:5本の試験片の1回目と、2回目の接炎による合計燃焼時間が50秒以内であり、かつ最大燃焼時間が10秒以内であり、燃焼による材料の滴下がない。
V-1:5本の試験片の1回目と、2回目の接炎による合計燃焼時間が250秒以内であり、かつ最大燃焼時間が30秒以内であり、燃焼による材料の滴下がない。
V-2:5本の試験片の1回目と、2回目の接炎による合計燃焼時間が250秒以内であり、かつ最大燃焼時間が30秒以内であること。(1) UL-94 vertical combustion test (V-0, V-1, V-2) with a test piece that has been allowed to stand for 12 hours or more under the conditions of 23 ° C. and 50% RH after producing a flame-retardant processed fiber product. A combustion test was conducted based on the standard). The size of the test piece was 127 mm in length and 12.7 mm in width. The flame contact was performed twice for each of the five test pieces, for a total of 10 times, and the average number of seconds and the maximum number of seconds for the flame extinguishing time were measured to make a judgment.
UL-94 Vertical Combustibility Test (V)
V-0: The total combustion time of the first and second flame contact of the five test pieces is within 50 seconds, the maximum combustion time is within 10 seconds, and there is no material dripping due to combustion.
V-1: The total combustion time of the first and second flame contact of the five test pieces is within 250 seconds, the maximum combustion time is within 30 seconds, and there is no material dripping due to combustion.
V-2: The total burning time of the first and second flame contact of the five test pieces is 250 seconds or less, and the maximum burning time is 30 seconds or less.
(2)防錆性
加工品作製後、23℃、50%RHの条件下に12時間以上静置した試験体をタテ:50mm、ヨコ:70mmに裁断し、真鍮(タテ:120mm、ヨコ:30mm、厚み:0.1mm)の主面に密着させ、60℃、95%RHの条件下に14日間静置して真鍮表面の錆の有無を確認した。表4と5において、評価結果を以下のように示す。
錆発生有:×
錆発生無:○(2) Rust prevention After manufacturing the processed product, the test piece left to stand at 23 ° C. and 50% RH for 12 hours or more was cut into vertical: 50 mm and horizontal: 70 mm, and brass (vertical: 120 mm, horizontal: 30 mm). (Thickness: 0.1 mm), the brass surface was allowed to stand for 14 days under the conditions of 60 ° C. and 95% RH, and the presence or absence of rust on the brass surface was confirmed. In Tables 4 and 5, the evaluation results are shown as follows.
With rust: ×
No rust: ○
(3)ブリーディング
加工品作製後、23℃、50%RHの条件下に12時間以上静置した試験体をタテ:50mm、ヨコ:70mmに裁断し、濾紙(タテ:100mm、ヨコ:60mm、No.2、東洋濾紙株式会社製)で挟み込み、60℃、95%RHの条件下に5日間静置し、加工品表面のブリーディングの有無を確認した。
表4と5において、評価結果を以下のように示す。
ブリーディング有:×
ブリーディング無:○(3) After producing the bleeding processed product, the test piece left to stand at 23 ° C. and 50% RH for 12 hours or more was cut into vertical: 50 mm, horizontal: 70 mm, and filter paper (vertical: 100 mm, horizontal: 60 mm, No.). 2. It was sandwiched between Toyo Filter Paper Co., Ltd.) and allowed to stand for 5 days under the conditions of 60 ° C. and 95% RH, and the presence or absence of bleeding on the surface of the processed product was confirmed.
In Tables 4 and 5, the evaluation results are shown as follows.
With bleeding: ×
No bleeding: ○
表4の結果から、本発明の繊維処理剤(実施例1~12)で処理された繊維加工品については、難燃性、防錆性のいずれにおいても共によく優れていることがわかる。また、ブリーディングについても十分に抑制されていることがわかる。
これに対して、表5に示すとおり、難燃剤(D)を含まない繊維処理剤を用いる場合(比較例1)は、難燃性が不十分であることがわかる。リン含有不飽和単量体(A)を含まず、且つ難燃剤(D)を繊維処理剤中のリン量が2.6%になるよう添加した繊維処理剤を用いる場合(比較例2)は、60℃、95%RHの条件下で顕著なブリーディングを引き起こすことがわかる。リン含有不飽和単量体(A)を含まず、且つ難燃剤(D)を繊維処理剤中のリン量が1.4%になるよう添加した繊維処理剤を用いる場合(比較例3)は、難燃性が不十分であることがわかる。防錆剤(C)を含まない繊維処理剤を用いる場合(比較例4)は、60℃、95%RHの条件下で防錆性が不十分であることがわかる。(メタ)アクリル酸及びイタコン酸からなる群から選択される少なくとも一種のカルボキシル基を有する不飽和単量体(b2)を重合性不飽和単量体(B)成分として含まない繊維処理剤を用いる場合(比較例5)は、顕著なブリーディングを引き起こすことがわかる。
(メタ)アクリル酸アルキルエステル不飽和単量体(b1)を重合性不飽和単量体(B)成分として含まない繊維処理剤を用いる場合(比較例6)は、防錆性が不十分であることがわかる。From the results in Table 4, it can be seen that the processed fiber products treated with the fiber treatment agents of the present invention (Examples 1 to 12) are excellent in both flame retardancy and rust prevention. It can also be seen that bleeding is sufficiently suppressed.
On the other hand, as shown in Table 5, it can be seen that the flame retardancy is insufficient when the fiber treatment agent containing no flame retardant (D) is used (Comparative Example 1). When a fiber treatment agent that does not contain the phosphorus-containing unsaturated monomer (A) and is added with the flame retardant (D) so that the amount of phosphorus in the fiber treatment agent is 2.6% is used (Comparative Example 2). , 60 ° C., 95% RH, found to cause significant bleeding. When a fiber treatment agent that does not contain the phosphorus-containing unsaturated monomer (A) and is added with the flame retardant (D) so that the amount of phosphorus in the fiber treatment agent is 1.4% is used (Comparative Example 3). , It turns out that the flame retardancy is insufficient. When a fiber treatment agent containing no rust preventive agent (C) is used (Comparative Example 4), it can be seen that the rust preventive property is insufficient under the conditions of 60 ° C. and 95% RH. A fiber treatment agent that does not contain an unsaturated monomer (b2) having at least one carboxyl group selected from the group consisting of (meth) acrylic acid and itaconic acid as a polymerizable unsaturated monomer (B) component is used. It can be seen that the case (Comparative Example 5) causes remarkable bleeding.
When a fiber treatment agent containing no (meth) acrylic acid alkyl ester unsaturated monomer (b1) as a component of the polymerizable unsaturated monomer (B) is used (Comparative Example 6), the rust resistance is insufficient. It turns out that there is.
本発明の繊維処理剤は、処理された繊維加工品が優れた難燃性や、高湿度条件下での優れた防錆性を有し、特に繊維処理用に好適である。また、本発明の繊維処理剤を用いた繊維加工品の製造方法は、難燃性、防錆性に優れる各種繊維加工品を製造するのに好適であり、この繊維加工品の製造方法を用いることによって、難燃性、防錆性に優れた繊維加工品を製造することができる。そして、この繊維加工品を使用することにより、難燃性、防錆性に優れる電子材料用緩衝材、家電用緩衝材、自動車内装緩衝材等の製造が可能となる。 The fiber treatment agent of the present invention is particularly suitable for fiber treatment because the treated fiber processed product has excellent flame retardancy and excellent rust prevention under high humidity conditions. Further, the method for producing a processed fiber product using the fiber treatment agent of the present invention is suitable for producing various processed fiber products having excellent flame retardancy and rust resistance, and the method for producing the processed fiber product is used. This makes it possible to manufacture a fiber processed product having excellent flame retardancy and rust resistance. By using this processed fiber product, it becomes possible to manufacture cushioning materials for electronic materials, cushioning materials for home appliances, cushioning materials for automobile interiors, etc., which are excellent in flame retardancy and rust resistance.
Claims (6)
防錆剤(C)と、
難燃剤(D)と、
を含む繊維処理剤であって、
前記重合性不飽和単量体(B)が、
(メタ)アクリル酸アルキルエステル不飽和単量体(b1)と、
(メタ)アクリル酸及びイタコン酸からなる群から選択される少なくとも一種の不飽和単量体(b2)と、
を含み、
前記防錆剤(C)は、カルボキシベンゾトリアゾールまたは1-[N,N-ビス(2-エチルヘキシル)アミノメチル]ベンゾトリアゾールを含み、
前記リン含有不飽和単量体(A)が、リン酸基又は亜リン酸基を有する単量体(a1)を含み、
前記重合性不飽和単量体(B)を、共重合体(P)中の全単量体に対し40質量%以上含有し、
前記重合性不飽和単量体(B)において、前記(メタ)アクリル酸アルキルエステル不飽和単量体(b1)及び前記(メタ)アクリル酸及びイタコン酸からなる群から選択される少なくとも一種の不飽和単量体(b2)との質量比(b1/b2)は、96/4~4/96であり、
前記防錆剤(C)を、全繊維処理剤に対し0.1~15質量%含有し、
前記難燃剤(D)を、全繊維処理剤に対し0.1~70質量%含有することを特徴とする繊維処理剤。 A copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B),
Rust inhibitor (C) and
With flame retardant (D),
It is a fiber treatment agent containing
The polymerizable unsaturated monomer (B) is
(Meta) acrylic acid alkyl ester unsaturated monomer (b1) and
At least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid,
Including
The rust inhibitor (C) contains carboxybenzotriazole or 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole .
The phosphorus-containing unsaturated monomer (A) contains a monomer (a1) having a phosphoric acid group or a phosphorous acid group.
The polymerizable unsaturated monomer (B) is contained in an amount of 40% by mass or more based on all the monomers in the copolymer (P).
In the polymerizable unsaturated monomer (B), at least one unsaturated substance selected from the group consisting of the (meth) acrylic acid alkyl ester unsaturated monomer (b1) and the (meth) acrylic acid and itaconic acid. The mass ratio (b1 / b2) with the saturated monomer (b2) is 96/4 to 4/96.
The rust preventive agent (C) is contained in an amount of 0.1 to 15% by mass based on the total fiber treatment agent.
A fiber treatment agent comprising the flame retardant (D) in an amount of 0.1 to 70% by mass with respect to the total fiber treatment agent.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016082714 | 2016-04-18 | ||
JP2016082714 | 2016-04-18 | ||
PCT/JP2017/014965 WO2017183535A1 (en) | 2016-04-18 | 2017-04-12 | Fiber treatment agent, method for producing processed fiber article, and processed fiber article |
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WO2010113796A1 (en) | 2009-03-31 | 2010-10-07 | 昭和高分子株式会社 | Resin composition and processed paper or fiber product treated therewith |
JP2012089375A (en) | 2010-10-20 | 2012-05-10 | Teijin Techno Products Ltd | Synthetic fiber for small-diameter electric wire cord |
WO2013047652A1 (en) | 2011-09-28 | 2013-04-04 | 豊田合成株式会社 | Coating material for airbag base fabric, and airbag base fabric |
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US20070135551A1 (en) * | 2005-12-12 | 2007-06-14 | Nissin Chemical Industry Co., Ltd. | Coating composition and vehicle interior material |
KR101226164B1 (en) * | 2012-06-14 | 2013-01-24 | 주식회사 우주염색 | Method for producing the electrically nylon conductive fiber |
JP6210327B2 (en) * | 2013-09-27 | 2017-10-11 | 豊田合成株式会社 | Airbag base fabric paint, airbag base fabric and manufacturing method thereof |
CN103911860B (en) * | 2013-12-27 | 2016-03-30 | 宁波市江东林清环保科技有限公司 | A kind of artificial fibre fire-proof flame-retarded agent |
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JP2012089375A (en) | 2010-10-20 | 2012-05-10 | Teijin Techno Products Ltd | Synthetic fiber for small-diameter electric wire cord |
WO2013047652A1 (en) | 2011-09-28 | 2013-04-04 | 豊田合成株式会社 | Coating material for airbag base fabric, and airbag base fabric |
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