JP4658820B2 - Inorganic fiber molded body and method for producing the same - Google Patents
Inorganic fiber molded body and method for producing the same Download PDFInfo
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- JP4658820B2 JP4658820B2 JP2006018472A JP2006018472A JP4658820B2 JP 4658820 B2 JP4658820 B2 JP 4658820B2 JP 2006018472 A JP2006018472 A JP 2006018472A JP 2006018472 A JP2006018472 A JP 2006018472A JP 4658820 B2 JP4658820 B2 JP 4658820B2
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- inorganic fiber
- inorganic
- coating layer
- mass
- molded body
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- 239000012784 inorganic fiber Substances 0.000 title claims description 215
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 239000011247 coating layer Substances 0.000 claims description 86
- 239000011230 binding agent Substances 0.000 claims description 54
- 239000011248 coating agent Substances 0.000 claims description 41
- 238000000576 coating method Methods 0.000 claims description 41
- 239000002002 slurry Substances 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 238000004090 dissolution Methods 0.000 claims description 34
- 239000000835 fiber Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 26
- 239000002504 physiological saline solution Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 101100116570 Caenorhabditis elegans cup-2 gene Proteins 0.000 claims description 2
- 101100116572 Drosophila melanogaster Der-1 gene Proteins 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 239000000843 powder Substances 0.000 description 36
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 14
- 229910052749 magnesium Inorganic materials 0.000 description 14
- 238000003860 storage Methods 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 235000021317 phosphate Nutrition 0.000 description 12
- 239000000395 magnesium oxide Substances 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 235000019832 sodium triphosphate Nutrition 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 229940126062 Compound A Drugs 0.000 description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- -1 inorganic compounds Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000005078 molybdenum compound Substances 0.000 description 5
- 150000002752 molybdenum compounds Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 150000003752 zinc compounds Chemical class 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 210000004072 lung Anatomy 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- QPLNUHHRGZVCLQ-UHFFFAOYSA-K aluminum;[oxido(phosphonooxy)phosphoryl] phosphate Chemical compound [Al+3].OP([O-])(=O)OP([O-])(=O)OP(O)([O-])=O QPLNUHHRGZVCLQ-UHFFFAOYSA-K 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- XEFUJGURFLOFAN-UHFFFAOYSA-N 1,3-dichloro-5-isocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=O)=C1 XEFUJGURFLOFAN-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical class C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YWSPSZGXUIDFDU-UHFFFAOYSA-N NC(=N)CCC=N Chemical compound NC(=N)CCC=N YWSPSZGXUIDFDU-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 description 2
- 210000001132 alveolar macrophage Anatomy 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- BYCHPAAGFQAEOD-UHFFFAOYSA-N ethenamine;hydrochloride Chemical compound Cl.NC=C BYCHPAAGFQAEOD-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- KWQCSIPJQQXVEQ-UHFFFAOYSA-N n'-ethenylprop-2-enimidamide;hydrochloride Chemical compound Cl.C=CC(N)=NC=C KWQCSIPJQQXVEQ-UHFFFAOYSA-N 0.000 description 2
- ILCQQHAOOOVHQJ-UHFFFAOYSA-N n-ethenylprop-2-enamide Chemical compound C=CNC(=O)C=C ILCQQHAOOOVHQJ-UHFFFAOYSA-N 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- SWRIXSGXHDICAR-UHFFFAOYSA-N [Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] SWRIXSGXHDICAR-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 210000000621 bronchi Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 210000004081 cilia Anatomy 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- FHCUBHNQRLFINC-UHFFFAOYSA-N dodecamagnesium hexasilicate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] FHCUBHNQRLFINC-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000002751 lymph Anatomy 0.000 description 1
- 210000001365 lymphatic vessel Anatomy 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910000386 magnesium trisilicate Inorganic materials 0.000 description 1
- 235000019793 magnesium trisilicate Nutrition 0.000 description 1
- 229940099273 magnesium trisilicate Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 210000001539 phagocyte Anatomy 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 210000003437 trachea Anatomy 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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Images
Description
本発明は、例えば、熱処理装置、工業窯炉内又は焼却炉内で、断熱材として使用される無機繊維質成形体、あるいは、特開平２００４−２６３８６０号公報等に記載されている、ディスクロールと呼ばれる高温物の運搬用ロールの基材又は特開平２００３−２９２３８０号公報等に記載されている、耐熱性セッターと呼ばれる高温物の運搬用治具の基材として使用される無機繊維質成形体、並びにその製造方法に関し、より具体的には、４０℃における生理食塩水溶解率が１％以上の無機繊維を主成分とする無機繊維質成形体に関する。以下、４０℃における生理食塩水溶解率が１％以上の無機繊維を、生体溶解性繊維とも記載する。 The present invention is, for example, an inorganic fiber molded body used as a heat insulating material in a heat treatment apparatus, an industrial kiln furnace or an incinerator, or a disk roll described in JP-A No. 2004-263860. An inorganic fiber molded body used as a base material for a high-temperature material transporting jig called a heat-resistant setter, which is described in a base material for a high-temperature material transporting roll or Japanese Patent Application Laid-Open No. 2003-292380, etc. More specifically, the present invention relates to an inorganic fiber molded body mainly composed of inorganic fibers having a physiological saline dissolution rate at 40 ° C. of 1% or more. Hereinafter, inorganic fibers having a physiological saline dissolution rate at 40 ° C. of 1% or more are also referred to as biosoluble fibers.
従来、無機繊維をバインダーで固めた繊維質成形体が、断熱材、ディスクロール、耐熱性セッターとして使用されており、該無機繊維としては、ガラス繊維、グラスウール、セラミックウール、ロックウール、アルミナ質繊維、ジルコニア質繊維、シリカ・アルミナ質繊維等（以下、従来の繊維質成形体の無機繊維等とも記載する。）が使用されていた。 Conventionally, a fibrous molded body in which inorganic fibers are hardened with a binder has been used as a heat insulating material, a disk roll, and a heat-resistant setter. Examples of the inorganic fibers include glass fibers, glass wool, ceramic wool, rock wool, and alumina fibers. , Zirconia fibers, silica / alumina fibers and the like (hereinafter also referred to as inorganic fibers of conventional fiber molded bodies) have been used.
この従来の繊維質成形体の無機繊維等は、人に吸入されて肺に侵入すると、肺胞マクロファージ（食細胞）により異物として取り囲まれ、繊毛がある場所（気管や気管支）まで運び込まれ痰とともに体外に排出されたり、リンパ液・リンパ管を経て肺胞表面から排出されたりする。しかし、異物の取り囲みにより肺胞マクロファージが刺激を受けたり、損傷を受けることもあり、それにより蛋白質分解酵素やコラーゲン繊維分解酵素が細胞から出て、これらの酵素の量が多くなると肺胞細胞が炎症を起こしたり、コラーゲン化を呈するようになることがある。こうした炎症を起こした細胞は抵抗力が弱まっており、細胞内の核の中にあるＤＮＡが損傷されやすくなるとともに、細胞の破壊と再製過程とが頻繁になり、異常細胞が出現する機会が多くなる。このように、従来の繊維質成形体の無機繊維では、人体への影響が懸念されてきた。 When the inorganic fibers of this conventional fiber molded body are inhaled by humans and enter the lungs, they are surrounded as foreign matter by alveolar macrophages (phagocytic cells) and are carried to the place where there is cilia (trachea and bronchi) together with wrinkles It is discharged out of the body, or discharged from the alveolar surface via lymph and lymphatic vessels. However, the alveolar macrophages may be stimulated or damaged due to the surrounding foreign material, and as a result, proteolytic enzymes and collagen fiber degrading enzymes are released from the cells, and if the amount of these enzymes increases, the alveolar cells May cause irritation or collagenation. These inflamed cells are less resistant, making it easier to damage the DNA in the cell's nucleus, and the frequent destruction and remanufacturing process, resulting in more opportunities for abnormal cells to appear. Become. As described above, there has been a concern about the influence on the human body in the inorganic fiber of the conventional fibrous molded body.
そのため、該従来の無機繊維質成形体の無機繊維等を使用しない無機繊維質成形体の開発が望まれていた。 Therefore, it has been desired to develop an inorganic fiber molded body that does not use inorganic fibers of the conventional inorganic fiber molded body.
４０℃における生理食塩水溶解率が１％以上の無機繊維（生体溶解性無機繊維）は、肺に吸入されても体内で溶解されやすい。そこで、従来の無機繊維質成形体の無機繊維等の代わりに、生体溶解性無機繊維を使用することが行われてきた。例えば、特開２００３−８２５６９号公報（特許文献１）には、ＳｉＯ２及びＣａＯを主成分とする無機繊維と、バインダーと、必要に応じて無機粉体とからなり、ＮａとＫの合計が４０００ｐｐｍ以下である無機繊維質成形体、及び該無機繊維、バインダー及び無機粉体を、水に入れ、攪拌してスラリーとし、次いで、成形し、乾燥する無機繊維質成形体の製造方法が開示されている。
無機繊維質成形体は、通常、大気中で保管されるので、保管中に大気中の水分を吸湿する。特に、輸出する際には、該無機繊維質成形体は、船底等の湿度が高い条件下で保管されるので、多くの水分を吸湿することになる。ところが、特許文献１に開示されている無機繊維質成形体は、主成分である無機繊維の一部が、水に溶解する性質を有しているため、吸湿した水分により該無機繊維が浸食され、該無機繊維が断裂したり、あるいは、該無機繊維が水分に溶解することにより生じるアルカリ成分が、有機バインダーを劣化させるため、該無機繊維質成形体の強度が低下するという問題が生じていた。このように、従来の生体溶解性無機繊維を主成分とする無機繊維質成形体では、保管中に劣化し、商品価値が低下するという問題があった。 Since the inorganic fibrous molded body is normally stored in the air, it absorbs moisture in the air during storage. In particular, when exporting, the inorganic fiber molded body absorbs a large amount of moisture because it is stored under conditions of high humidity such as the ship bottom. However, since the inorganic fiber molded body disclosed in Patent Document 1 has a property that a part of the inorganic fiber as a main component is dissolved in water, the inorganic fiber is eroded by moisture absorbed. In addition, the alkali component generated when the inorganic fiber is torn or the inorganic fiber is dissolved in moisture deteriorates the organic binder, which causes a problem that the strength of the inorganic fibrous molded body is reduced. . As described above, the conventional inorganic fiber molded body mainly composed of biosoluble inorganic fibers is deteriorated during storage and has a problem that the commercial value is lowered.
また、無機繊維質成形体は、通常、特許文献１に開示されている無機繊維質成形体の製造方法のように、無機繊維及びバインダーを水に分散させたスラリーを調製し、次いで、該スラリー中の水を、吸引ろ過する吸引成形を行い得られる。すなわち、無機繊維質成形体中の無機繊維は、必ず、水と接触する。そのため、特許文献１に開示されている無機繊維質成形体の製造方法には、無機繊維質成形体の製造時に、無機繊維が劣化するとういう問題もあった。 In addition, the inorganic fibrous molded body is usually prepared as a slurry in which inorganic fibers and a binder are dispersed in water, as in the method for producing an inorganic fibrous molded body disclosed in Patent Document 1, and then the slurry. It is possible to perform suction molding for suction filtration of the water therein. That is, the inorganic fibers in the inorganic fiber molded body always come into contact with water. Therefore, the method for producing an inorganic fiber molded body disclosed in Patent Document 1 also has a problem that the inorganic fiber deteriorates during the production of the inorganic fiber molded body.
従って、本発明の目的は、４０℃における生理食塩水溶解率が１％以上の無機繊維（生体溶解性無機繊維）の成形体であって、保管時に劣化が少ない無機繊維質成形体及びその製造方法、並びに製造時に生体溶解性無機繊維の劣化が少ない無機繊維質成形体の製造方法を提供することにある。 Accordingly, an object of the present invention is a molded body of inorganic fibers (biosoluble inorganic fibers) having a physiological saline solubility at 40 ° C. of 1% or more, and an inorganic fiber molded body with little deterioration during storage, and its production It is an object of the present invention to provide a method and a method for producing an inorganic fiber molded body with little degradation of biosoluble inorganic fibers during production.
かかる実情において、本発明者らは、鋭意検討を行った結果、（１）４０℃における生理食塩水溶解率が１％以上である無機繊維（ｂ）の表面を、被覆層で被覆して得られる、被覆層形成無機繊維（ａ）は、該被覆層が水分の保護膜として働くので、水と接触しても劣化し難いこと、そのため、（２）該被覆層形成無機繊維（ａ）を成形して得られる無機繊維質成形体は、保管中に吸湿しても、劣化が少ないことなどを見出し、本発明を完成させるに至った。 Under such circumstances, the present inventors have conducted extensive studies, and as a result, (1) the surface of inorganic fiber (b) having a physiological saline dissolution rate at 40 ° C. of 1% or more is obtained by coating with a coating layer. The coating layer-forming inorganic fiber (a) is not easily deteriorated even when it comes into contact with water because the coating layer functions as a moisture protective film. Therefore, (2) the coating layer-forming inorganic fiber (a) The inorganic fibrous molded body obtained by molding has been found to be less deteriorated even if it absorbs moisture during storage, and the present invention has been completed.
すなわち、本発明は、被覆層形成無機繊維（ａ）及びバインダーを含有し、
該被覆層形成無機繊維（ａ）の４０℃における生理食塩水溶解率が１％以上であり、
該被覆層形成無機繊維（ａ）が、無機繊維（ｂ）の表面に被覆層が形成されている繊維であり、
該無機繊維（ｂ）が、ＳｉＯ ２ ７５〜８０質量％、ＣａＯ＋ＭｇＯ １９〜２５質量％、Ａｌ ２ Ｏ ３ １〜３質量％を含む無機繊維であり、
該被覆層が、リン酸塩で形成されていること、
を特徴とする無機繊維質成形体を提供するものである。
That is, this invention contains a coating layer forming inorganic fiber (a) and a binder,
Saline dissolution rate in the 40 ° C. of the coating layer forming the inorganic fiber (a) is Ri der 1% or more,
The coating layer-forming inorganic fiber (a) is a fiber having a coating layer formed on the surface of the inorganic fiber (b),
The inorganic fiber (b) is an inorganic fiber containing 75 to 80% by mass of SiO 2 , 19 to 25% by mass of CaO + MgO, and 1 to 3% by mass of Al 2 O 3 ,
The coating layer is formed of phosphate;
The present invention provides an inorganic fibrous shaped article characterized by the following.
また、本発明は、溶媒に、被覆層形成剤を混合し、次いで、４０℃における生理食塩水溶解率が１％以上である無機繊維（ｂ）及びバインダーを混合し、被覆層形成無機繊維（ａ）を含有するスラリーを得るスラリー製造工程、及び該スラリー中の溶媒を、吸引ろ過し、無機繊維質成形体を得る脱水成形工程を有し、
該無機繊維（ｂ）が、ＳｉＯ ２ ７５〜８０質量％、ＣａＯ＋ＭｇＯ １９〜２５質量％、Ａｌ ２ Ｏ ３ １〜３質量％を含む無機繊維であり、
該被覆層形成剤が、リン酸塩であること、
を特徴とする無機繊維質成形体の製造方法を提供するものである。
Moreover, this invention mixes a coating layer formation agent with a solvent, and then mixes the inorganic fiber (b) and the binder whose physiological saline dissolution rate in 40 degreeC is 1% or more, and a coating layer formation inorganic fiber ( slurry preparation step of obtaining a slurry containing a), and the solvent in the slurry, is filtered off with suction, it has a dehydration molding to obtain an inorganic fibrous molded body,
The inorganic fiber (b) is an inorganic fiber containing 75 to 80% by mass of SiO 2 , 19 to 25% by mass of CaO + MgO, and 1 to 3% by mass of Al 2 O 3 ,
The coating layer forming agent is a phosphate;
The manufacturing method of the inorganic fiber molded object characterized by these is provided.
本発明によれば、生体溶解性無機繊維の成形体であって、保管時に劣化が少ない無機繊維質成形体及びその製造方法、並びに製造時に生体溶解性無機繊維の劣化が少ない無機繊維質成形体の製造方法を提供することができる。 According to the present invention, a molded body of biologically soluble inorganic fibers, an inorganic fibrous molded body with little deterioration during storage, a method for producing the same, and an inorganic fibrous molded body with less degradation of biologically soluble inorganic fibers during production The manufacturing method of can be provided.
本発明の無機繊維質成形体は、被覆層形成無機繊維（ａ）及びバインダーを含有する。 The inorganic fibrous molded body of the present invention contains a coating layer forming inorganic fiber (a) and a binder.
該被覆層形成無機繊維（ａ）は、表面に被覆層が形成されている繊維であり、且つ４０℃における生理食塩水溶解率が１％以上の無機繊維である。 The coating layer-forming inorganic fiber (a) is a fiber having a coating layer formed on the surface, and is an inorganic fiber having a physiological saline dissolution rate at 40 ° C. of 1% or more.
該被覆層形成無機繊維（ａ）の４０℃における生理食塩水溶解率が１％以上であるためには、該被覆層形成無機繊維（ａ）の該被覆層以外の部分、すなわち、該被覆層が形成される前の無機繊維も、４０℃における生理食塩水溶解率が１％以上であることが必要である。従って、該被覆層形成無機繊維（ａ）は、４０℃における生理食塩水溶解率が１％以上である無機繊維（ｂ）の表面に、該被覆層が形成されている繊維である。なお、本発明において該無機繊維（ｂ）とは、該被覆層が形成されておらず、且つ４０℃における生理食塩水溶解率が１％以上である無機繊維を指す。 In order that the physiological saline dissolution rate at 40 ° C. of the coating layer-forming inorganic fiber (a) is 1% or more, a portion other than the coating layer of the coating layer-forming inorganic fiber (a), that is, the coating layer It is necessary that the inorganic fiber before the formation of is also 1% or higher in the physiological saline dissolution rate at 40 ° C. Therefore, the coating layer-forming inorganic fiber (a) is a fiber in which the coating layer is formed on the surface of the inorganic fiber (b) having a physiological saline dissolution rate at 40 ° C. of 1% or more. In the present invention, the inorganic fiber (b) refers to an inorganic fiber in which the coating layer is not formed and the physiological saline dissolution rate at 40 ° C. is 1% or more.
該被覆層形成無機繊維（ａ）及び該無機繊維（ｂ）の生理食塩水溶解率の測定方法について説明する。先ず、無機繊維を２００メッシュ以下に粉砕した試料１ｇ及び生理食塩水１５０ｍｌを三角フラスコ（３００ｍｌ）に入れ、４０℃のインキュベーターに設置する。次に、該三角フラスコに、毎分１２０回転の水平振盪を５０時間継続して与える。振盪後、ろ過し、得られたろ液中に含有されているケイ素、マグネシウム、カルシウム及びアルミニウムについて、各元素の濃度（ｍｇ／Ｌ）を、ＩＣＰ発光分析にて測定する。そして、該ろ液中の各元素の濃度及び溶解前の無機繊維中の各元素の含有量（質量％）から、下記式（１）により、生理食塩水溶解率Ｃ（％）を算出する。なお、ＩＣＰ発光分析により得られる各元素の濃度を、ケイ素元素の濃度：ａ１（ｍｇ／Ｌ）、マグネシウム元素の濃度：ａ２（ｍｇ／Ｌ）、カルシウム元素の濃度：ａ３（ｍｇ／Ｌ）及びアルミニウム元素の濃度ａ４（ｍｇ／Ｌ）とし、溶解前の無機繊維中の各元素の含有量を、ケイ素元素の含有量：ｂ１（質量％）、マグネシウム元素の含有量：ｂ２（質量％）、カルシウム元素の含有量：ｂ３（質量％）及びアルミニウム元素の含有量：ｂ４（質量％）とする。
Ｃ（％）＝｛ろ液量（Ｌ）×（ａ１＋ａ２＋ａ３＋ａ４）×１００｝／｛溶解前の無機繊維の量（ｍｇ）×（ｂ１＋ｂ２＋ｂ３＋ｂ４）／１００｝ （１）
A method for measuring the dissolution rate of physiological saline in the coating layer-forming inorganic fiber (a) and the inorganic fiber (b) will be described. First, 1 g of a sample obtained by pulverizing inorganic fibers to 200 mesh or less and 150 ml of physiological saline are placed in an Erlenmeyer flask (300 ml) and placed in an incubator at 40 ° C. The Erlenmeyer flask is then subjected to horizontal shaking at 120 revolutions per minute for 50 hours. After shaking, the mixture is filtered, and the concentration (mg / L) of each element is measured by ICP emission analysis for silicon, magnesium, calcium and aluminum contained in the obtained filtrate. Then, from the concentration of each element in the filtrate and the content (mass%) of each element in the inorganic fiber before dissolution, the physiological saline dissolution rate C (%) is calculated by the following formula (1). The concentration of each element obtained by ICP emission analysis is as follows: silicon element concentration: a1 (mg / L), magnesium element concentration: a2 (mg / L), calcium element concentration: a3 (mg / L) and The aluminum element concentration a4 (mg / L), the content of each element in the inorganic fiber before dissolution, silicon element content: b1 (mass%), magnesium element content: b2 (mass%), Calcium element content: b3 (mass%) and aluminum element content: b4 (mass%).
C (%) = {filtrate amount (L) × (a1 + a2 + a3 + a4) × 100} / {amount of inorganic fiber before dissolution (mg) × (b1 + b2 + b3 + b4) / 100} (1)
該無機繊維（ｂ）としては、例えば、特開２０００−２２００３７号公報、特開２００２−６８７７７号公報、特開２００３−７３９２６号公報、あるいは特開２００３−２１２５９６号公報に記載されている無機繊維が挙げられる。具体的には、ＳｉＯ２及びＣａＯの合計含有量が８５質量％以上であり、０．５〜３．０質量％のＭｇＯ及び２．０〜８．０質量％のＰ２Ｏ５を含有し、かつドイツ危険物質規制による発癌性指数（ＫＩ値）が４０以上である無機繊維、ＳｉＯ２、ＭｇＯ及びＴｉＯ２を必須成分とする無機繊維、ＳｉＯ２、ＭｇＯ及び酸化マンガンを必須成分とする無機繊維、ＳｉＯ２ ５２〜７２質量％、Ａｌ２Ｏ３ ３質量％未満、ＭｇＯ ０〜７質量％、ＣａＯ ７．５〜９．５質量％、Ｂ２Ｏ３ ０〜１２質量％、ＢａＯ ０〜４質量％、ＳｒＯ ０〜３．５質量％、Ｎａ２Ｏ １０〜２０．５質量％、Ｋ２Ｏ ０．５〜４．０質量％及びＰ２Ｏ５ ０〜５質量％を含む無機繊維、ＳｉＯ２ ７５〜８０質量％、ＣａＯ＋ＭｇＯ １９〜２５質量％、Ａｌ２Ｏ３ １〜３質量％を含む無機繊維である。 Examples of the inorganic fiber (b) include inorganic fibers described in JP-A No. 2000-220037, JP-A No. 2002-68777, JP-A No. 2003-73926, or JP-A No. 2003-212596. Is mentioned. Specifically, the total content of SiO 2 and CaO is 85% by mass or more, containing 0.5 to 3.0% by mass of MgO and 2.0 to 8.0% by mass of P 2 O 5. Inorganic fibers having a carcinogenicity index (KI value) of 40 or more according to German hazardous substance regulations, inorganic fibers containing SiO 2 , MgO and TiO 2 as essential components, inorganic containing SiO 2 , MgO and manganese oxide as essential components fiber, SiO 2 52-72 wt%, Al less than 2 O 3 3 wt%, MgO 0 to 7 wt%, CaO 7.5 to 9.5 wt%, B 2 O 3 0~12 wt%, BaO 0 to Inorganic fiber containing 4% by mass, SrO 0-3.5% by mass, Na 2 O 10-20.5% by mass, K 2 O 0.5-4.0% by mass and P 2 O 5 0-5% by mass , SiO 2 75-80 mass%, CaO + MgO 19 to 25 wt% Inorganic fibers containing Al 2 O 3 1~3 wt%.
該被覆層形成無機繊維（ａ）の表面に形成されている該被覆層は、水に難溶であり且つ生理食塩水には溶け易い。従って、表面に該被覆層が形成されている該被覆層形成無機繊維（ａ）は、水に難溶であり且つ生理食塩水には溶け易く、該被覆層が形成されていない該無機繊維（ｂ）に比べ、水への溶解率（以下、水溶解率とも記載する。）が低くなる。すなわち、該被覆層は、該被覆層形成無機繊維（ａ）の保護膜として働く。 The coating layer formed on the surface of the coating layer-forming inorganic fiber (a) is hardly soluble in water and easily soluble in physiological saline. Accordingly, the coating layer-forming inorganic fiber (a) having the coating layer formed on the surface thereof is hardly soluble in water and easily dissolved in physiological saline, and the inorganic fiber (the coating layer is not formed) ( Compared with b), the water dissolution rate (hereinafter also referred to as water dissolution rate) is low. That is, the coating layer serves as a protective film for the coating layer-forming inorganic fiber (a).
該被覆層形成無機繊維（ａ）の表面に該被覆層が形成されているか否かは次のようにして判断することができる。先ず、表面に該被覆層が形成されている生体溶解性無機繊維（以下、試料１とも記載する。）と、該被覆層が形成されていない生体溶解性無機繊維（以下、試料２とも記載する。）とを用意する。そして、該試料１を２００メッシュ以下に粉砕した試料１ｇ及び蒸留水１５０ｍｌを三角フラスコ（３００ｍｌ）に入れ、４０℃のインキュベーターに設置する。次に、該三角フラスコに、毎分１２０回転の水平振盪を５０時間継続して与える。振盪後、ろ過し、得られたろ液中に含有されているケイ素、マグネシウム、カルシウム及びアルミニウムについて、各元素の濃度（ｍｇ／Ｌ）を、ＩＣＰ発光分析にて測定する。そして、該ろ液中の各元素の濃度及び溶解前の無機繊維中の各元素の含有量（質量％）から、下記式（２）により、蒸留水溶解率Ｄ（％）を算出する。なお、ＩＣＰ発光分析により得られる各元素の濃度を、ケイ素元素の濃度：ｅ１（ｍｇ／Ｌ）、マグネシウム元素の濃度：ｅ２（ｍｇ／Ｌ）、カルシウム元素の濃度：ｅ３（ｍｇ／Ｌ）及びアルミニウム元素の濃度ｅ４（ｍｇ／Ｌ）とし、溶解前の無機繊維中の各元素の含有量を、ケイ素元素の含有量：ｂ１（質量％）、マグネシウム元素の含有量：ｂ２（質量％）、カルシウム元素の含有量：ｂ３（質量％）及びアルミニウム元素の含有量：ｂ４（質量％）とする。
Ｄ（％）＝｛ろ液量（Ｌ）×（ｅ１＋ｅ２＋ｅ３＋ｅ４）×１００｝／｛溶解前の無機繊維の量（ｍｇ）×（ｂ１＋ｂ２＋ｂ３＋ｂ４）／１００｝ （２）
該試料２のついても、該試料１に代えて該試料２とする以外は、該試料１と同様の方法で、蒸留水溶解率Ｄ（％）を算出する。そして、該試料１の蒸留水溶解率Ｄ（％）の値が、該試料２の蒸留水溶解率Ｄ（％）の値より小さい場合、すなわち、下記式（３）：
該試料１の蒸留水溶解率Ｄ（％）＜該試料２の蒸留水溶解率Ｄ（％） （３）
を満たせば、該被覆層形成無機繊維（ａ）の表面に該被覆層が形成されていると判断する。
Whether or not the coating layer is formed on the surface of the coating layer-forming inorganic fiber (a) can be determined as follows. First, a biosoluble inorganic fiber (hereinafter also referred to as sample 1) having the coating layer formed on its surface and a biosoluble inorganic fiber (hereinafter also referred to as sample 2) having no coating layer formed thereon. )). Then, 1 g of the sample 1 pulverized to 200 mesh or less and 150 ml of distilled water are placed in an Erlenmeyer flask (300 ml) and placed in an incubator at 40 ° C. The Erlenmeyer flask is then subjected to horizontal shaking at 120 revolutions per minute for 50 hours. After shaking, the mixture is filtered, and the concentration (mg / L) of each element is measured by ICP emission analysis for silicon, magnesium, calcium and aluminum contained in the obtained filtrate. And the distilled water dissolution rate D (%) is calculated from the concentration of each element in the filtrate and the content (mass%) of each element in the inorganic fiber before dissolution by the following formula (2). The concentration of each element obtained by ICP emission analysis is as follows: silicon element concentration: e1 (mg / L), magnesium element concentration: e2 (mg / L), calcium element concentration: e3 (mg / L) and The aluminum element concentration e4 (mg / L), the content of each element in the inorganic fiber before dissolution, the silicon element content: b1 (mass%), the magnesium element content: b2 (mass%), Calcium element content: b3 (mass%) and aluminum element content: b4 (mass%).
D (%) = {filtrate amount (L) × (e1 + e2 + e3 + e4) × 100} / {amount of inorganic fiber before dissolution (mg) × (b1 + b2 + b3 + b4) / 100} (2)
With respect to Sample 2, the distilled water dissolution rate D (%) is calculated in the same manner as Sample 1, except that Sample 2 is used instead of Sample 1. And when the value of the distilled water solubility D (%) of the sample 1 is smaller than the value of the distilled water solubility D (%) of the sample 2, that is, the following formula (3):
Distilled water dissolution rate D (%) of sample 1 <Distilled water dissolution rate D (%) of sample 2 (3)
Is satisfied, it is determined that the coating layer is formed on the surface of the coating layer-forming inorganic fiber (a).
該被覆層形成無機繊維（ａ）の該被覆層を形成する物質としては、リン酸塩、モリブデン化合物、亜鉛化合物等の無機化合物、ポリアミジン化合物、エチレンイミン化合物等の有機化合物が挙げられる。該リン酸塩としては、トリポリリン酸アルミニウム、トリポリリン酸二水素アルミニウム、メタリン酸アルミニウム、リン酸亜鉛、リン酸カルシウム等が挙げられ、該モリブデン化合物としては、モリブデン酸亜鉛、モリブデン酸アルミニウム、モリブデン酸カルシウム、リンモリブデン酸カルシウム、リンモリブデン酸アルミニウム等が挙げられ、該亜鉛化合物としては酸化亜鉛が挙げられ、該ポリアミジン化合物としては、アクリルアミド、アクリロニトリル、Ｎ−ビニルアクリルアミジン塩酸塩、Ｎ−ビニルアクリルアミド、ビニルアミン塩酸塩、Ｎ−ビニルホルムアミド共重合体等が挙げられ、該エチレンイミン化合物としては、アミノエチレン、ジメチレンイミン等が挙げられる。 As a substance which forms this coating layer of this coating layer forming inorganic fiber (a), organic compounds, such as inorganic compounds, such as a phosphate, a molybdenum compound, a zinc compound, a polyamidine compound, and an ethyleneimine compound, are mentioned. Examples of the phosphate include aluminum tripolyphosphate, aluminum dihydrogen triphosphate, aluminum metaphosphate, zinc phosphate, and calcium phosphate. Examples of the molybdenum compound include zinc molybdate, aluminum molybdate, calcium molybdate, phosphorus, and the like. Examples of the zinc compound include zinc oxide. Examples of the polyamidine compound include acrylamide, acrylonitrile, N-vinylacrylamidine hydrochloride, N-vinylacrylamide, and vinylamine hydrochloride. N-vinylformamide copolymer and the like, and examples of the ethyleneimine compound include aminoethylene, dimethyleneimine and the like.
該被覆層を形成する物質がリン酸塩の場合、該被覆層は、通常、薄膜と言うより、むしろ該無機繊維（ｂ）の表面に、リン酸塩の微粒子が密に付着又は吸着している状態である。モリブデン化合物、亜鉛化合物等の該リン酸塩以外の無機化合物、ポリアミジン化合物、エチレンイミン化合物等の有機化合物物についても同様である。 When the material forming the coating layer is a phosphate, the coating layer is usually not a thin film, but rather a fine particle of phosphate is adhered or adsorbed on the surface of the inorganic fiber (b). It is in a state. The same applies to inorganic compounds other than the phosphate such as molybdenum compounds and zinc compounds, and organic compounds such as polyamidine compounds and ethyleneimine compounds.
該被覆層が、リンを含有する場合、本発明の無機繊維質成形体中のリンの含有量は、酸化物換算で、好ましくは０．１〜１０質量％、特に好ましくは０．３〜６質量％、更に好ましくは０．５〜３質量％である。該リンの含有量が、上記範囲にあることにより、保管時に、無機繊維質成形体が劣化し難くなる。 When the coating layer contains phosphorus, the content of phosphorus in the inorganic fibrous formed body of the present invention is preferably 0.1 to 10% by mass, particularly preferably 0.3 to 6 in terms of oxide. It is 0.5 mass%, More preferably, it is 0.5-3 mass%. When the phosphorus content is in the above range, the inorganic fibrous molded body is hardly deteriorated during storage.
また、該被覆層がリンを含有する場合には、該被覆層は、珪素、亜鉛、カルシウム、マグネシウムを含有しても良い。この時、該被覆層中のこれらの物質の含有量は、酸化物換算で、珪素が０．０１〜５０質量％、亜鉛が０．０１〜３０質量％、カルシウムが０．０１〜１５質量％、マグネシウムが０．０１〜１０質量％であることが好ましく、珪素が１０〜４０質量％、亜鉛が１０〜２５質量％、カルシウムが５〜１０質量％、マグネシウムが２〜７質量％であることが特に好ましい。特に、マグネシウムを含有することが好ましい。 Moreover, when this coating layer contains phosphorus, this coating layer may contain silicon, zinc, calcium, and magnesium. At this time, the content of these substances in the coating layer is 0.01 to 50% by mass of silicon, 0.01 to 30% by mass of zinc, and 0.01 to 15% by mass of calcium in terms of oxide. Magnesium is preferably 0.01 to 10% by mass, silicon is 10 to 40% by mass, zinc is 10 to 25% by mass, calcium is 5 to 10% by mass, and magnesium is 2 to 7% by mass. Is particularly preferred. In particular, it is preferable to contain magnesium.
該被覆層形成無機繊維（ａ）は、該無機繊維（ｂ）の表面が、該被覆層で完全に覆われていることが好ましいが、極一部に被覆が欠落していてもよい。該被覆層形成無機繊維（ａ）の表面に形成されている該被覆層は、電子顕微鏡あるいは組成分析など、公知の方法により確認することができる。 In the coating layer-forming inorganic fiber (a), the surface of the inorganic fiber (b) is preferably completely covered with the coating layer, but the coating may be missing in a very small part. The coating layer formed on the surface of the coating layer-forming inorganic fiber (a) can be confirmed by a known method such as an electron microscope or composition analysis.
また、該被覆層形成無機繊維（ａ）は、１種又は２種以上の組み合わせのいずれでもよい。すなわち、該被覆層を形成する物質又は該被覆層が形成されている該無機繊維（ｂ）のいずれか一方又は双方が異なる被覆層形成無機繊維（ａ）を組合わせることもできる。 Further, the coating layer-forming inorganic fiber (a) may be one type or a combination of two or more types. That is, the coating layer forming inorganic fiber (a) in which either one or both of the substance forming the coating layer and the inorganic fiber (b) on which the coating layer is formed can be combined.
該被覆層形成無機繊維（ａ）の平均繊維径は１〜５０μｍ、好ましくは１．５〜１０μｍ、特に好ましくは２〜６μｍである。該平均繊維径が、１μｍ未満だと繊維が破断し易くなるので、無機繊維質成形体の強度が低くなり易く、また、５０μｍを超えると無機繊維質成形体の密度が低くなるため、無機繊維質成形体の強度が低くなり易い。また、該被覆層形成無機繊維（ａ）の平均繊維長は１〜２００ｍｍ、好ましくは２〜５０ｍｍ、特に好ましくは１０〜５０ｍｍである。該平均繊維長が、上記範囲内にあることにより、適切な密度を有する無機繊維質成形体が得易くなる。 The average fiber diameter of the coating layer-forming inorganic fiber (a) is 1 to 50 μm, preferably 1.5 to 10 μm, particularly preferably 2 to 6 μm. If the average fiber diameter is less than 1 μm, the fibers are likely to break, so the strength of the inorganic fibrous molded body tends to be low. If the average fiber diameter exceeds 50 μm, the density of the inorganic fibrous molded body is low. The strength of the molded product tends to be low. Moreover, the average fiber length of this coating layer forming inorganic fiber (a) is 1-200 mm, Preferably it is 2-50 mm, Most preferably, it is 10-50 mm. When the average fiber length is within the above range, an inorganic fibrous molded body having an appropriate density can be easily obtained.
該被覆層形成無機繊維（ａ）は、４０℃における生理食塩水溶解率が１％以上である。該被覆層形成無機繊維（ａ）の、４０℃における生理食塩水溶解率が、１％以上であることにより、肺に吸収されても生体内で溶解され易い。一方、該被覆層形成無機繊維（ａ）の、４０℃における生理食塩水溶解率が、１％未満だと、肺に吸入されても生体内で溶解され難いので、該被覆層形成無機繊維（ａ）は肺に蓄積し、各種の呼吸器疾患を発生させる原因となることが懸念される。 The covering layer-forming inorganic fiber (a) has a physiological saline dissolution rate at 40 ° C. of 1% or more. When the covering layer-forming inorganic fiber (a) has a physiological saline dissolution rate at 40 ° C. of 1% or more, it is easily dissolved in vivo even if it is absorbed into the lungs. On the other hand, if the physiological saline dissolution rate at 40 ° C. of the coating layer-forming inorganic fiber (a) is less than 1%, the coating layer-forming inorganic fiber ( It is feared that a) accumulates in the lung and causes various respiratory diseases.
本発明の無機繊維質成形体中、該被覆層形成無機繊維（ａ）の含有量は、６５〜９９．８質量％、好ましくは７０〜９５質量％、特に好ましくは８０〜９０質量％である。なお、該被覆層形成無機繊維（ａ）の一部を後述する耐熱性粉末に置き換える場合は、該被覆層形成無機繊維（ａ）及び該耐熱性粉末の合計の含有量が、６５〜９９．５質量％、好ましくは７０〜９５質量％、特に好ましくは８０〜９０質量％である。 In the inorganic fiber molded body of the present invention, the content of the coating layer-forming inorganic fiber (a) is 65 to 99.8% by mass, preferably 70 to 95% by mass, particularly preferably 80 to 90% by mass. . In addition, when replacing a part of this coating layer formation inorganic fiber (a) with the heat resistant powder mentioned later, the total content of this coating layer formation inorganic fiber (a) and this heat resistant powder is 65-99. 5 mass%, preferably 70 to 95 mass%, particularly preferably 80 to 90 mass%.
該バインダーとしては、無機バインダー又は有機バインダーのいずれもでもよく、あるいは、無機バインダー及び有機バインダーの組合せでも良い。該無機バインダーとしては、特に制限されず、例えば、アニオン性のコロイダルシリカ、カチオン性のコロイダルシリカ等のコロイダルシリカ、ヒュームドシリカ、ジルコニアゾル、チタニアゾル、アルミナゾル、ベントナイト等が挙げられ、有機バインダーとしては、特に制限されず、例えば、アクリル樹脂、澱粉、ポリアクリルアミド等が挙げられる。施工時に壁面等の形状への追随性が高い無機繊維質成形体、すなわち、軟らかい無機繊維質成形体に使用される該バインダーとしては、アクリル樹脂が好ましい。また、使用温度が高い無機繊維質成形体又は硬い無機繊維質成形体に使用される該バインダーとしては、該無機バインダーと、澱粉又はポリアクリルアミドの組合わせが好ましい。 As the binder, either an inorganic binder or an organic binder may be used, or a combination of an inorganic binder and an organic binder may be used. The inorganic binder is not particularly limited, and examples thereof include colloidal silica such as anionic colloidal silica and cationic colloidal silica, fumed silica, zirconia sol, titania sol, alumina sol, bentonite, and the like. There are no particular restrictions, and examples include acrylic resin, starch, and polyacrylamide. An acrylic resin is preferable as the binder used in the inorganic fiber molded body having high followability to the shape of the wall surface during construction, that is, the soft inorganic fiber molded body. Moreover, as this binder used for the inorganic fiber molded object or hard inorganic fiber molded object with a high operating temperature, the combination of this inorganic binder and starch or polyacrylamide is preferable.
本発明の無機繊維質成形体中、該無機バインダーの含有量は、０．０５〜２０質量％、好ましくは２〜１５質量％、特に好ましくは３〜１０質量％である。該無機バインダーの含有量が、０．０５質量％未満だと、工業炉等内での使用による無機繊維質成形体の強度向上効果が得られ難く、また、２０質量％を超えると、脱水成形時の濾水性が悪くなり、製造効率が悪くなり易い。また、該有機バインダーの含有量は、０．０３〜１５質量％、好ましくは０．１〜１０質量％、特に好ましくは０．５〜５質量％である。該有機バインダーの含有量が０．０３質量％未満だと、脱水成形後の無機繊維質成形体の強度が低くなり易く、１５質量％を超えると無機繊維質成形体からの燃焼ガスの排出が多くなる。 In the inorganic fibrous molded body of the present invention, the content of the inorganic binder is 0.05 to 20% by mass, preferably 2 to 15% by mass, and particularly preferably 3 to 10% by mass. When the content of the inorganic binder is less than 0.05% by mass, it is difficult to obtain an effect of improving the strength of the inorganic fibrous molded body by use in an industrial furnace or the like. The drainage at the time deteriorates, and the production efficiency tends to deteriorate. Moreover, content of this organic binder is 0.03-15 mass%, Preferably it is 0.1-10 mass%, Most preferably, it is 0.5-5 mass%. When the content of the organic binder is less than 0.03% by mass, the strength of the inorganic fibrous molded body after dehydration molding tends to be low, and when it exceeds 15% by mass, combustion gas is discharged from the inorganic fibrous molded body. Become more.
また、本発明の無機繊維質成形体では、該被覆層形成無機繊維（ａ）の一部を、耐熱性粉末に置き換えることができる。本発明の無機繊維質成形体は、該被覆層形成無機繊維（ａ）の一部が、該耐熱性粉末で置き換えられることにより、すなわち、該耐熱性粉末を含有することにより、耐火性が高くなる。該耐熱性粉末としては、例えば、シリカ、アルミナ、チタニア、ジルコニア、窒化ケイ素、炭化ケイ素等のセラミックス粉末、カーボンブラック等の炭素粉末等が挙げられ、これらのうち、好ましくはシリカ、アルミナ、窒化ケイ素、炭化ケイ素等のセラミックス粉末、カーボンブラック等の炭素粉末であり、特に好ましくはシリカ、アルミナ、窒化ケイ素、炭化ケイ素等のセラミックス粉末である。 Moreover, in the inorganic fiber molded object of this invention, a part of this coating layer formation inorganic fiber (a) can be replaced with a heat resistant powder. The inorganic fibrous molded body of the present invention has high fire resistance when a part of the coating layer-forming inorganic fiber (a) is replaced by the heat-resistant powder, that is, by containing the heat-resistant powder. Become. Examples of the heat-resistant powder include ceramic powder such as silica, alumina, titania, zirconia, silicon nitride, and silicon carbide, and carbon powder such as carbon black. Among these, silica, alumina, and silicon nitride are preferable. Ceramic powders such as silicon carbide and carbon powders such as carbon black, and ceramic powders such as silica, alumina, silicon nitride and silicon carbide are particularly preferable.
該耐熱性粉末の平均粒子径は、０．１〜１００μｍ、好ましくは０．２〜５０μｍ、特に好ましくは０．２〜１０μｍである。該平均粒子径が、０．１μｍ未満だと、乾燥又は焼成時に、無機繊維質成形体が割れ易くなり、また、該平均粒子径が、１００μｍを超えると、無機繊維質成形体の強度が低くなり易い。 The average particle diameter of the heat resistant powder is 0.1 to 100 μm, preferably 0.2 to 50 μm, and particularly preferably 0.2 to 10 μm. When the average particle diameter is less than 0.1 μm, the inorganic fibrous molded body is easily broken during drying or firing, and when the average particle diameter exceeds 100 μm, the strength of the inorganic fibrous molded body is low. Easy to be.
本発明の無機繊維質成形体中の該被覆層形成無機繊維（ａ）の一部を、該耐熱性粉末に置き換える場合、本発明の無機繊維質成形体中の該被覆層形成無機繊維（ａ）と該耐熱性粉末の質量比（被覆層形成無機繊維（ａ）：耐熱性粉末）は、好ましくは９５：５〜２５：７５、特に好ましくは９０：１０〜５０：５０、更に好ましくは８０：２０〜７０：３０である。該被覆層形成無機繊維（ａ）と該耐熱性粉末の質量比が、上記範囲にあることにより、該耐熱性粉末による耐熱性の向上効果が得られ易く、且つ無機繊維質成形体の耐スポーリング性が良好である。 When a part of the coating layer-forming inorganic fibers (a) in the inorganic fiber molded body of the present invention is replaced with the heat-resistant powder, the coating layer-forming inorganic fibers (a) in the inorganic fiber molded body of the present invention ) And the mass ratio of the heat-resistant powder (coating layer forming inorganic fiber (a): heat-resistant powder) is preferably 95: 5 to 25:75, particularly preferably 90:10 to 50:50, more preferably 80. : 20-70: 30. When the mass ratio of the coating layer-forming inorganic fiber (a) and the heat-resistant powder is in the above range, the effect of improving the heat resistance by the heat-resistant powder can be easily obtained, and the resistance of the inorganic fiber molded article to Good polling performance.
本発明の無機繊維質成形体では、水に難溶性の該被覆層が、該無機繊維（ｂ）と水分の接触を遮断する保護膜として働くので、本発明の無機繊維質成形体は、保管中に、大気中の水分を吸湿しても、劣化が少ない。さらに詳細に説明すると、該被覆層が、該被覆層形成無機繊維（ａ）中の該被覆層より内部の部分、すなわち、該無機繊維（ｂ）に相当する部分と水分の接触を遮断するので、該被覆層を形成させることにより、水分の吸湿を原因とする無機繊維質成形体の劣化を少なくすることができ、また、繊維が該水分により浸食されて、断裂するのを防ぐことができる。更には、バインダーとして、有機バインダーが使用されている場合、該被覆層を形成させることにより、該水分が繊維を溶解して、アルカリ成分が生じるのを防ぐことができるので、該溶出液が、該有機バインダーを劣化させ、無機繊維質成形体から繊維が脱落するのを防ぐことができる。従って、本発明の無機繊維質成形体は、保管中の劣化が少ない。 In the inorganic fibrous molded body of the present invention, the coating layer that is sparingly soluble in water serves as a protective film that blocks contact between the inorganic fibers (b) and moisture. Even if moisture in the atmosphere is absorbed, there is little deterioration. More specifically, since the coating layer blocks contact of moisture with a portion inside the coating layer in the coating layer-forming inorganic fiber (a), that is, a portion corresponding to the inorganic fiber (b). By forming the coating layer, it is possible to reduce deterioration of the inorganic fibrous molded body due to moisture absorption, and it is possible to prevent the fiber from being eroded by the moisture and torn. . Furthermore, when an organic binder is used as the binder, by forming the coating layer, it is possible to prevent the moisture from dissolving the fiber and generating an alkali component. The organic binder can be deteriorated to prevent the fibers from falling off from the inorganic fibrous molded body. Therefore, the inorganic fibrous molded body of the present invention is less deteriorated during storage.
本発明の無機繊維質成形体の製造方法は、溶媒に、被覆層形成剤を混合し、次いで、４０℃における生理食塩水溶解率が１％以上である無機繊維（ｂ）及びバインダーを混合し、被覆層形成無機繊維（ａ）を含有するスラリーを得るスラリー製造工程、及び該スラリー中の溶媒を、吸引ろ過し、無機繊維質成形体を得る脱水成形工程を有する。 In the method for producing an inorganic fibrous molded body of the present invention, a coating layer forming agent is mixed in a solvent, and then an inorganic fiber (b) having a physiological saline dissolution rate at 40 ° C. of 1% or more and a binder are mixed. And a slurry production step for obtaining a slurry containing the coating layer-forming inorganic fibers (a), and a dehydration molding step for obtaining a inorganic fibrous shaped body by suction filtration of the solvent in the slurry.
該スラリー製造工程では、先ず、溶媒に、被覆層形成剤を混合し、被覆層形成剤を含有する混合液を調製する。該被覆層形成剤には、無機化合物の被覆層形成剤と有機化合物の被覆層形成剤がある。 In the slurry production step, first, a coating layer forming agent is mixed with a solvent to prepare a mixed solution containing the coating layer forming agent. The coating layer forming agent includes an inorganic compound coating layer forming agent and an organic compound coating layer forming agent.
該被覆層形成剤としては、リン酸塩、モリブデン化合物、亜鉛化合物等の無機化合物、ポリアミジン化合物、エチレンイミン化合物等の有機化合物が挙げられる。該リン酸塩としては、トリポリリン酸アルミニウム、トリポリリン酸二水素アルミニウム、メタリン酸アルミニウム、リン酸亜鉛、リン酸カルシウム等が挙げられ、該モリブデン化合物としては、モリブデン酸亜鉛、モリブデン酸アルミニウム、モリブデン酸カルシウム、リンモリブデン酸カルシウム、リンモリブデン酸アルミニウム等が挙げられ、該亜鉛化合物としては酸化亜鉛が挙げられ、該ポリアミジン化合物としては、アクリルアミド、アクリロニトリル、Ｎ−ビニルアクリルアミジン塩酸塩、Ｎ−ビニルアクリルアミド、ビニルアミン塩酸塩、Ｎ−ビニルホルムアミド共重合体等が挙げられ、該エチレンイミン化合物としては、アミノエチレン、ジメチレンイミン等が挙げられる。 Examples of the coating layer forming agent include inorganic compounds such as phosphates, molybdenum compounds and zinc compounds, and organic compounds such as polyamidine compounds and ethyleneimine compounds. Examples of the phosphate include aluminum tripolyphosphate, aluminum dihydrogen triphosphate, aluminum metaphosphate, zinc phosphate, and calcium phosphate. Examples of the molybdenum compound include zinc molybdate, aluminum molybdate, calcium molybdate, phosphorus, and the like. Examples of the zinc compound include zinc oxide. Examples of the polyamidine compound include acrylamide, acrylonitrile, N-vinylacrylamidine hydrochloride, N-vinylacrylamide, and vinylamine hydrochloride. N-vinylformamide copolymer and the like, and examples of the ethyleneimine compound include aminoethylene, dimethyleneimine and the like.
また、該被覆層形成剤として該リン酸塩を混合する場合には、更に、珪素、亜鉛、カルシウム又はマグネシウムを有する化合物（以下、これらを総称して、珪素等を有する化合物Ａとも記載する。）を、該被覆層形成剤として混合することができる。該珪素等を有する化合物Ａは、酸化物、水酸化物、炭酸塩等が挙げられ、化合物の形態は特に制限されず、具体的には、酸化珪素、珪酸カルシウム、メタ珪酸カルシウム、珪酸マグネシウム、六珪酸マグネシウム、四珪酸マグネシウム、三珪酸マグネシウム、酸化亜鉛、酸化カルシウム、水酸化カルシウム、炭酸カルシウム、酸化マグネシウム、水酸化マグネシウム、炭酸マグネシウム、ホウ酸マグネシウムが挙げられる。 Further, when the phosphate is mixed as the coating layer forming agent, it is further described as a compound having silicon, zinc, calcium or magnesium (hereinafter collectively referred to as compound A having silicon or the like). ) Can be mixed as the coating layer forming agent. Compound A having silicon and the like includes oxides, hydroxides, carbonates and the like, and the form of the compound is not particularly limited. Specifically, silicon oxide, calcium silicate, calcium metasilicate, magnesium silicate, Examples include magnesium hexasilicate, magnesium tetrasilicate, magnesium trisilicate, zinc oxide, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, and magnesium borate.
該溶媒としては、特に制限されないが、水及び極性有機溶媒が挙げられ、該極性有機溶媒としては、エタノール、プロパノール等の１価のアルコール類、エチレングリコール等の２価のアルコール類が挙げられる。これらのうち、水が、作業環境の悪化がなく、環境への負荷がない点で好ましい。また、該水としては特に制限されず、蒸留水、イオン交換水、水道水、地下水、工業用水等が挙げられる。 The solvent is not particularly limited, and examples thereof include water and a polar organic solvent. Examples of the polar organic solvent include monovalent alcohols such as ethanol and propanol, and divalent alcohols such as ethylene glycol. Among these, water is preferable in that there is no deterioration of the working environment and there is no burden on the environment. Moreover, it does not restrict | limit especially as this water, Distilled water, ion-exchange water, tap water, groundwater, industrial water etc. are mentioned.
該溶媒に、該被覆層形成剤を混合して得られる、該被覆層形成剤を含有する混合液は、該被覆層形成剤が該溶媒に溶解している溶液であっても、該被覆層形成剤が該溶媒に固体のまま分散している懸濁液であってもよい。 The mixed liquid containing the coating layer forming agent obtained by mixing the coating layer forming agent with the solvent may be a solution in which the coating layer forming agent is dissolved in the solvent. It may be a suspension in which the forming agent is dispersed as a solid in the solvent.
次いで、該被覆層形成剤を含有する混合液に、該無機繊維（ｂ）及び該バインダーを混合し、該被覆層形成無機繊維（ａ）を含有するスラリーを得る。 Next, the inorganic fiber (b) and the binder are mixed in a mixed solution containing the coating layer forming agent to obtain a slurry containing the coating layer forming inorganic fiber (a).
本発明の無機繊維質成形体の製造方法に係る無機繊維（ｂ）は、前記本発明の無機繊維質成形体に係る無機繊維（ｂ）と同様である。 The inorganic fiber (b) which concerns on the manufacturing method of the inorganic fiber molded object of this invention is the same as the inorganic fiber (b) which concerns on the said inorganic fiber molded object of this invention.
また、本発明の無機繊維質成形体の製造方法に係る無機繊維（ｂ）の平均繊維径は、１〜５０μｍ、好ましくは１．５〜１０μｍ、特に好ましくは２〜６μｍである。該平均繊維径が、１μｍ未満だと無機繊維が破断し易くなるので、無機繊維質成形体の強度が低くなり易く、また、５０μｍを超えると無機繊維質成形体の密度が低くなるので、無機繊維質成形体の強度が低くなり易い。また、該無機繊維の平均繊維長は１〜２００ｍｍ、好ましくは２〜５０ｍｍ、特に好ましくは１０〜５０ｍｍである。該平均繊維長が、上記範囲内にあることにより、適切な密度を有する無機繊維質成形体が得易くなる。 Moreover, the average fiber diameter of the inorganic fiber (b) which concerns on the manufacturing method of the inorganic fiber molded object of this invention is 1-50 micrometers, Preferably it is 1.5-10 micrometers, Most preferably, it is 2-6 micrometers. If the average fiber diameter is less than 1 μm, the inorganic fibers are likely to break, so the strength of the inorganic fibrous molded body tends to be low, and if it exceeds 50 μm, the density of the inorganic fibrous molded body is low. The strength of the fibrous molded body tends to be low. The average fiber length of the inorganic fibers is 1 to 200 mm, preferably 2 to 50 mm, particularly preferably 10 to 50 mm. When the average fiber length is within the above range, an inorganic fibrous molded body having an appropriate density can be easily obtained.
本発明の無機繊維質成形体の製造方法に係るバインダーは、前記本発明の無機繊維質成形体に係るバインダーと同様である。 The binder which concerns on the manufacturing method of the inorganic fiber molded object of this invention is the same as the binder which concerns on the said inorganic fiber molded object of this invention.
本発明の無機繊維質成形体の製造方法に係るバインダーの形態としては、固形物、懸濁液又は溶液等、いずれでもよく、特に制限されない。 As a form of the binder which concerns on the manufacturing method of the inorganic fiber molded object of this invention, any may be sufficient as a solid substance, a suspension, or a solution, and it does not restrict | limit.
また、該無機繊維（ｂ）の一部を、耐熱性粉末に置き換えることができる。該無機繊維の一部が、該耐熱性粉末で置き換えられることにより、耐火性が高くなる。 Moreover, a part of the inorganic fiber (b) can be replaced with heat-resistant powder. Fire resistance is enhanced by replacing a part of the inorganic fibers with the heat-resistant powder.
該スラリー製造工程に係る耐熱性粉末は、前記本発明の無機繊維質成形体に係る耐熱性粉末と同様である。 The heat-resistant powder according to the slurry production process is the same as the heat-resistant powder according to the inorganic fibrous molded body of the present invention.
該被覆層形成剤を含有する混合液に、該無機繊維（ｂ）及び該バインダーを混合する順序は、特に制限されず、該無機繊維（ｂ）が先であっても、該バインダーが先であってもよく、また、同時に混合してもよい。 The order in which the inorganic fiber (b) and the binder are mixed with the mixed solution containing the coating layer forming agent is not particularly limited, and even if the inorganic fiber (b) is first, the binder is first. It may be present or mixed at the same time.
このように、該被覆層形成剤を含有する混合液に、該無機繊維（ｂ）を混合することにより、該無機繊維（ｂ）の表面に、該被覆層形成剤が付着し、該被覆層が形成される。そして、該被覆層の形成は、該無機繊維（ｂ）の混合後、速やかに起こるので、該無機繊維質成形体の製造中に、該無機繊維（ｂ）が、水と接触して、劣化するのを防ぐことができる。 Thus, by mixing the inorganic fiber (b) with the mixed solution containing the coating layer forming agent, the coating layer forming agent adheres to the surface of the inorganic fiber (b), and the coating layer Is formed. And since formation of this coating layer occurs rapidly after mixing of this inorganic fiber (b), this inorganic fiber (b) contacts with water and deteriorates during manufacture of this inorganic fiber molded object. Can be prevented.
該スラリー製造工程における各成分の混合量について説明する。該被覆層形成剤の混合量は、該溶媒に混合する該被覆層形成剤、該無機繊維（ｂ）、該バインダー及び該耐熱性粉末の混合量の合計を１００質量％とした場合、該被覆層形成剤の質量割合が、０．０５〜１０質量％、好ましくは０．３〜６質量％、特に好ましくは０．５〜３質量％となる量である。該被覆剤形成剤の混合量が、上記範囲にあることにより、保管中に劣化が少ない無機繊維質成形体が得られるという効果が高くなる。なお、該バインダーが、溶媒に分散された懸濁液又は溶液の形態の場合、溶媒分を除いた固形分の質量が、上記混合量の合計を算出するための該バインダーの混合量である。また、該被覆層形成無機繊維（ａ）を含有するスラリーが、該耐熱性粉末を含有しない場合があるが、この場合は、該被覆層形成剤、該無機繊維（ｂ）及び該バインダーの合計の混合量を１００質量％とする。これらについては、以下同様である。 The mixing amount of each component in the slurry production process will be described. The mixing amount of the coating layer forming agent is such that the total mixing amount of the coating layer forming agent mixed with the solvent, the inorganic fiber (b), the binder and the heat resistant powder is 100% by mass. The mass ratio of the layer forming agent is 0.05 to 10% by mass, preferably 0.3 to 6% by mass, particularly preferably 0.5 to 3% by mass. When the mixing amount of the coating agent-forming agent is within the above range, the effect of obtaining an inorganic fibrous molded body with little deterioration during storage is enhanced. When the binder is in the form of a suspension or solution dispersed in a solvent, the mass of the solid content excluding the solvent is the mixed amount of the binder for calculating the total mixed amount. In addition, the slurry containing the coating layer-forming inorganic fiber (a) may not contain the heat-resistant powder. In this case, the total of the coating layer-forming agent, the inorganic fiber (b), and the binder The mixing amount is set to 100% by mass. The same applies to the following.
また、該被覆層形成剤として該リン酸塩を混合する場合、該珪素等を有する化合物Ａを混合することができるが、該珪素等を有する化合物Ａの混合量は、該被覆層形成剤（該リン酸塩及び該珪素等を有する化合物Ａの合計量）の総量を１００質量％として、酸化物換算で、珪素が０．０１〜５０質量％、亜鉛が０．０１〜３０質量％、カルシウムが０．０１〜１５質量％、マグネシウムが０．０１〜１０質量％であることが好ましく、珪素が１０〜４０質量％、亜鉛が１０〜２５質量％、カルシウムが５〜１０質量％、マグネシウムが２〜７質量％であることが特に好ましい。特に、該珪素等を有する化合物Ａとしては、マグネシウムを含有する化合物が好ましい。 In addition, when the phosphate is mixed as the coating layer forming agent, the compound A having silicon or the like can be mixed, but the mixing amount of the compound A having silicon or the like can be mixed with the coating layer forming agent ( The total amount of the compound A having the phosphate and the silicon) is 100% by mass, in terms of oxide, 0.01 to 50% by mass of silicon, 0.01 to 30% by mass of zinc, calcium Is 0.01 to 15% by mass, magnesium is preferably 0.01 to 10% by mass, silicon is 10 to 40% by mass, zinc is 10 to 25% by mass, calcium is 5 to 10% by mass, and magnesium is It is particularly preferably 2 to 7% by mass. In particular, the compound A containing silicon or the like is preferably a compound containing magnesium.
該耐熱性粉末を混合しない場合は、該無機繊維（ｂ）の混合量は、該溶媒に混合する該被覆層形成剤、該無機繊維（ｂ）及び該バインダーの混合量の合計を１００質量％とした場合、該無機繊維（ｂ）の質量割合が、６５〜９９．８質量％、好ましくは７０〜９５質量％、特に好ましくは８０〜９０質量％となる量である。また、該無機繊維（ｂ）の一部を該耐熱性粉末に置き換える場合は、該無機繊維（ｂ）及び該耐熱性粉末の合計の混合量は、該被覆層形成剤、該無機繊維（ｂ）、該バインダー及び該耐熱性粉末の混合量の合計を１００質量％とした場合、該無機繊維（ｂ）及び該耐熱性粉末の合計の質量割合が、６５〜９９．５質量％、好ましくは７０〜９５質量％、特に好ましくは８０〜９０質量％となる量である。 When the heat-resistant powder is not mixed, the mixing amount of the inorganic fiber (b) is 100% by mass of the total amount of the coating layer forming agent mixed with the solvent, the inorganic fiber (b) and the binder. In this case, the mass ratio of the inorganic fiber (b) is 65 to 99.8 mass%, preferably 70 to 95 mass%, particularly preferably 80 to 90 mass%. When a part of the inorganic fiber (b) is replaced with the heat-resistant powder, the total amount of the inorganic fiber (b) and the heat-resistant powder depends on the coating layer forming agent and the inorganic fiber (b ), When the total amount of the binder and the heat-resistant powder is 100% by mass, the total mass ratio of the inorganic fiber (b) and the heat-resistant powder is 65 to 99.5% by mass, preferably The amount is 70 to 95% by mass, particularly preferably 80 to 90% by mass.
該無機バインダーを混合する場合、該無機バインダーの混合量は、該溶媒に混合する該被覆層形成剤、該無機繊維（ｂ）、該バインダー及び該耐熱性粉末の混合量の合計を１００質量％とした場合、該無機バインダーの質量割合が、０．０５〜２０質量％、好ましくは２〜１５質量％、特に好ましくは３〜１０質量％となる量である。該無機バインダーの質量割合が、０．０５質量％未満だと、工業炉等内での使用による無機繊維質成形体の強度向上効果が得られ難く、また、２０質量％を超えると、脱水成形時の濾水性が悪くなり、製造効率が悪くなり易い。また、該有機バインダーを混合する場合、該有機バインダーの混合量は、該溶媒に混合する該被覆層形成剤、該無機繊維（ｂ）、該バインダー及び該耐熱性粉末の混合量の合計を１００質量％とした場合、該無機バインダーの質量割合が、０．０３〜１５質量％、好ましくは０．１〜１０質量％、特に好ましくは０．５〜５質量％となる量である。該有機バインダーの質量割合が、０．０３質量％未満だと、成形乾燥後の無機繊維質成形体の強度が低くなりやすく、１５質量％を超えると無機繊維質成形体からの燃焼ガスの排出が多くなる。 When mixing the inorganic binder, the mixing amount of the inorganic binder is 100% by mass of the total mixing amount of the coating layer forming agent mixed with the solvent, the inorganic fibers (b), the binder and the heat-resistant powder. In this case, the mass ratio of the inorganic binder is 0.05 to 20% by mass, preferably 2 to 15% by mass, particularly preferably 3 to 10% by mass. If the mass ratio of the inorganic binder is less than 0.05% by mass, it is difficult to obtain an effect of improving the strength of the inorganic fibrous molded article by use in an industrial furnace or the like, and if it exceeds 20% by mass, dehydration molding is performed. The drainage at the time deteriorates, and the production efficiency tends to deteriorate. In addition, when the organic binder is mixed, the mixing amount of the organic binder is the total of the mixing amount of the coating layer forming agent, the inorganic fiber (b), the binder and the heat-resistant powder mixed in the solvent. In the case of mass%, the mass ratio of the inorganic binder is 0.03 to 15 mass%, preferably 0.1 to 10 mass%, particularly preferably 0.5 to 5 mass%. When the mass ratio of the organic binder is less than 0.03 mass%, the strength of the inorganic fibrous molded body after molding and drying tends to be low, and when it exceeds 15 mass%, combustion gas is discharged from the inorganic fibrous molded body. Will increase.
該無機繊維（ｂ）の一部を、該耐熱性粉末に置き換える場合、該被覆層形成無機繊維（ａ）を含有するスラリー中の該無機繊維（ｂ）と該耐熱性粉末の質量比（無機繊維（ｂ）：耐熱性粉末）は、好ましくは９５：５〜２５：７５、特に好ましくは９０：１０〜５０：５０、更に好ましくは８０：２０〜７０：３０である。該無機繊維（ｂ）と該耐熱性粉末の質量比が、上記範囲にあることにより、該耐熱性粉末による耐熱性の向上効果が得られ易く、且つ無機繊維質成形体の耐スポーリング性が良好である。 When a part of the inorganic fiber (b) is replaced with the heat-resistant powder, the mass ratio of the inorganic fiber (b) and the heat-resistant powder in the slurry containing the coating layer-forming inorganic fiber (a) (inorganic The fiber (b): heat resistant powder) is preferably 95: 5 to 25:75, particularly preferably 90:10 to 50:50, and more preferably 80:20 to 70:30. When the mass ratio of the inorganic fiber (b) and the heat-resistant powder is in the above range, the effect of improving the heat resistance by the heat-resistant powder can be easily obtained, and the spalling resistance of the inorganic fibrous molded body can be improved. It is good.
該被覆層形成無機繊維（ａ）を含有するスラリーのスラリー濃度は、好ましくは０．１〜１０質量％、特に好ましくは０．３〜８質量％、更に好ましくは０．５〜３質量％である。該スラリー濃度が、０．１質量％未満だと該脱水成形工程で除去する水の量が多くなり過ぎるので、非効率であり、また、１０質量％を超えると、スラリーに固形分が均一に分散し難くなる。なお、本発明において、スラリー濃度とは、該被覆層形成無機繊維（ａ）を含有するスラリー中に占める固形分の質量割合（質量％）を示す。また、該固形分には、該被覆層形成剤も含まれる。 The slurry concentration of the slurry containing the coating layer-forming inorganic fiber (a) is preferably 0.1 to 10% by mass, particularly preferably 0.3 to 8% by mass, and more preferably 0.5 to 3% by mass. is there. If the slurry concentration is less than 0.1% by mass, the amount of water to be removed in the dehydration molding process becomes excessive, which is inefficient. If it exceeds 10% by mass, the slurry has a uniform solid content. Difficult to disperse. In addition, in this invention, a slurry density | concentration shows the mass ratio (mass%) of the solid content which occupies in the slurry containing this coating layer forming inorganic fiber (a). The solid content includes the coating layer forming agent.
該スラリー製造工程中、該溶媒及び該スラリーの温度は、５〜５０℃、好ましくは１０〜４０℃、特に好ましくは１５〜３０℃である。 During the slurry production process, the temperature of the solvent and the slurry is 5 to 50 ° C, preferably 10 to 40 ° C, and particularly preferably 15 to 30 ° C.
該脱水成形工程は、該被覆層形成無機繊維（ａ）を含有するスラリー中の該溶媒を除去し、次いで、乾燥し、目的とする製品形状を有する無機繊維質成形体を得る工程である。該被覆層形成無機繊維（ａ）を含有するスラリー中の該溶媒が水の場合は、該スラリー中の水を脱水し、次いで、乾燥し、目的とする製品形状を有する無機繊維質成形体を得る工程、すなわち、該スラリーを脱水成形し、無機繊維質成形体を得る工程である。なお、本発明の無機繊維質成形体の製造方法では、該溶媒として水が使用されることが多いので、脱水成形の文言を用いた。 The dehydration molding step is a step of removing the solvent in the slurry containing the coating layer-forming inorganic fibers (a) and then drying to obtain an inorganic fibrous molded body having a desired product shape. When the solvent in the slurry containing the coating layer-forming inorganic fiber (a) is water, the water in the slurry is dehydrated and then dried to obtain an inorganic fibrous molded body having a desired product shape. The step of obtaining, that is, the step of dehydrating the slurry to obtain an inorganic fibrous shaped body. In addition, in the manufacturing method of the inorganic fiber molded object of this invention, since water is often used as this solvent, the word of dehydration molding was used.
該スラリー中の該溶媒の除去（該溶媒が水の場合は、水の脱水）は、例えば、底部に網が設置された成形型中に該スラリーを流し込み、該溶媒（該溶媒が水の場合は、水）を吸引することにより行われる。 The removal of the solvent in the slurry (when the solvent is water, dehydration of water) is performed, for example, by pouring the slurry into a mold having a net installed at the bottom, and the solvent (when the solvent is water). Is performed by sucking water).
次いで、脱水物を乾燥機中で加熱して、乾燥させる。該乾燥の際の乾燥温度は、４０〜１８０℃、好ましくは６０〜１５０℃、特に好ましくは８０〜１２０℃である。 The dehydrate is then heated in a dryer and dried. The drying temperature during the drying is 40 to 180 ° C, preferably 60 to 150 ° C, particularly preferably 80 to 120 ° C.
本発明の無機繊維質成形体の製造方法によれば、該被覆層形成剤を含有する混合液に、該無機繊維（ｂ）を混合して、該無機繊維（ｂ）の表面に被覆層を形成させるので、無機繊維質成形体の製造中に、該無機繊維（ｂ）が、溶媒と接触して劣化するのを防ぐことができる。 According to the method for producing an inorganic fiber molded body of the present invention, the inorganic fiber (b) is mixed with the mixed solution containing the coating layer forming agent, and the coating layer is formed on the surface of the inorganic fiber (b). Since it forms, it can prevent that this inorganic fiber (b) contacts with a solvent and deteriorates during manufacture of an inorganic fiber molded object.
また、本発明の無機繊維質成形体の製造方法は、本発明の無機繊維質成形体の製造に好適に用いられる。すなわち、本発明の無機繊維質成形体の製造方法によれば、保管の際に劣化が少ない無機繊維質成形体を製造することができる。 Moreover, the manufacturing method of the inorganic fiber molded object of this invention is used suitably for manufacture of the inorganic fiber molded object of this invention. That is, according to the method for manufacturing an inorganic fiber molded body of the present invention, an inorganic fiber molded body with little deterioration during storage can be manufactured.
次に、実施例を挙げて本発明を更に具体的に説明するが、これは単に例示であって、本発明を制限するものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.
（実施例１）
（被覆層形成無機繊維（ａ）を含有するスラリーの製造）
先ず、水に、被覆層形成剤として、予めトリポリリン酸二水素アルミニウム１．１質量％、酸化珪素０．６質量％、酸化マグネシウム０．１質量％を混合した混合物を加え、被覆層形成剤を含有する混合液を得た。次いで、該混合液に、無機繊維（ｂ）８９．３質量％、無機バインダーとしてコロイダルシリカ４．９質量％、有機バインダーとして澱粉２．２質量％及びカチオン性紙力増強剤１．８質量％を加え、更に、スラリー濃度が３質量％となるように、水を加え、攪拌し、スラリーを得た。なお、該被覆層形成剤を含有する混合液に、該無機繊維（ｂ）を混合しても、該スラリーのｐＨは高くならなかった。
・無機繊維（ｂ）：ＳｉＯ２ ７５〜８０質量％、ＣａＯ＋ＭｇＯ １９〜２５質量％、Ａｌ２Ｏ３ １〜３質量％、平均繊維径４μｍ、平均繊維長５．０ｍｍ、４０℃における生理食塩水溶解率５．９％
・無機バインダー：３０％コロイダルシリカ、「シリカドール３０」（日本化学工業社製）、固形分が３０％の懸濁液、固形分の平均粒子径１５ｎｍ、ｐＨ１０．０
・有機バインダー：澱粉、「ペトロサイズＪ」（日澱化学社製）
・有機バインダー：カチオン性紙力増強剤、「ポリストロン３１１」（荒川化学工業社製）、カチオン性、不揮発分１０質量％、ｐＨ４．２〜４．８、粘度５００〜１５００ｃｐｓ
Example 1
(Production of slurry containing coating layer-forming inorganic fiber (a))
First, as a coating layer forming agent, a mixture prepared by previously mixing 1.1% by mass of aluminum dihydrogen triphosphate, 0.6% by mass of silicon oxide, and 0.1% by mass of magnesium oxide is added to water. A mixed liquid containing was obtained. Next, the mixed solution was mixed with 89.3% by weight of inorganic fiber (b), 4.9% by weight of colloidal silica as an inorganic binder, 2.2% by weight of starch as an organic binder, and 1.8% by weight of a cationic paper strength enhancer. Further, water was added and stirred so that the slurry concentration became 3% by mass to obtain a slurry. In addition, even if this inorganic fiber (b) was mixed with the liquid mixture containing this coating layer forming agent, the pH of the slurry did not increase.
Inorganic fiber (b): SiO 2 75-80% by mass, CaO + MgO 19-25% by mass, Al 2 O 3 1-3% by mass, average fiber diameter 4 μm, average fiber length 5.0 mm, physiological saline at 40 ° C. Dissolution rate 5.9%
Inorganic binder: 30% colloidal silica, “Silica Doll 30” (manufactured by Nippon Chemical Industry Co., Ltd.), suspension with a solid content of 30%, average particle size of solid content 15 nm, pH 10.0
・ Organic binder: Starch, “Petrosize J” (manufactured by Nissho Chemical Co., Ltd.)
Organic binder: cationic paper strength enhancer, “Polystron 311” (manufactured by Arakawa Chemical Industries, Ltd.), cationic, non-volatile content 10% by mass, pH 4.2 to 4.8, viscosity 500 to 1500 cps
（吸引ろ過）
上記のようにして得られたスラリーを、脱水成形し１１０℃で乾燥することにより、密度２５０ｋｇ／ｍ３の無機繊維質成形体（試料Ａ０とする。）を得た。
(Suction filtration)
The slurry obtained as described above was dehydrated and dried at 110 ° C. to obtain an inorganic fibrous molded body (sample A0) having a density of 250 kg / m 3 .
（無機繊維質成形体の長期保管試験）
上記のようにして得た無機繊維質成形体（試料Ａ０）を、湿度９０ＲＨ、４０℃の室内で、所定の期間保管した後（１ヶ月保管後の試料を試料Ａ１、３ヶ月保管後の試料を試料Ａ３とする。）に、加熱線収縮率及び曲げ強度の測定を行った。その結果を表１に示す。
(Long-term storage test of inorganic fiber molded body)
After storing the inorganic fiber molded body (sample A0) obtained as described above in a room at a humidity of 90 RH and 40 ° C. for a predetermined period (sample after storage for 1 month is sample A1, sample after storage for 3 months) Was taken as sample A3), and the measurement of the heating linear shrinkage rate and bending strength was performed. The results are shown in Table 1.
（１）加熱線収縮率
上記のようにして得られた無機繊維質成形体を、電気炉中１１００℃で２４時間加熱し、加熱後の無機繊維質成形体の長さを測定する。加熱線収縮率は、加熱前の無機繊維質成形体の長さをＸｍｍ、加熱後の長さをＹｍｍとし、次式により求める。
加熱線収縮率（％）＝｛（Ｘ−Ｙ）／Ｘ｝×１００
(1) Heat shrinkage rate The inorganic fibrous molded body obtained as described above is heated in an electric furnace at 1100 ° C. for 24 hours, and the length of the heated inorganic fibrous molded body is measured. The heating line shrinkage rate is obtained by the following equation, where Xmm is the length of the inorganic fiber molded body before heating and Ymm is the length after heating.
Heating linear shrinkage rate (%) = {(XY) / X} × 100
（２）曲げ強度
試料Ａ０、Ａ１及びＡ３の曲げ強度を、３点曲げ強度試験機を用いて、ヘッドスピード１０ｍｍ／分の速度で荷重を加え、破断荷重を測定し、次式により算出した。
曲げ強度（ＭＰａ）＝｛３×最大荷重（Ｎ）×下部支点間距離（ｍｍ）｝／｛２×無機繊維質成形体の幅（ｍｍ）×（無機繊維質成形体の厚さ（ｍｍ））２｝
(2) Bending strength The bending strength of samples A0, A1 and A3 was calculated using the following equation by applying a load at a head speed of 10 mm / min using a three-point bending strength tester and measuring the breaking load.
Bending strength (MPa) = {3 × maximum load (N) × distance between lower fulcrums (mm)} / {2 × width of inorganic fiber molded body (mm) × (thickness of inorganic fiber molded body (mm) 2 }
（実施例２〜４、比較例１）
各成分の混合量を表１に示す量とする以外は、実施例１と同様の方法で行った。その結果を表１に示す。
(Examples 2 to 4, Comparative Example 1)
The same procedure as in Example 1 was performed except that the mixing amount of each component was the amount shown in Table 1. The results are shown in Table 1.
（参考例）
室温下、予め混合したトリポリリン酸二水素アルミニウム２．３質量％、酸化珪素１．３質量％及び酸化マグネシウム０．２質量％を被覆層形成剤として水に添加し攪拌して白濁液を得た。次いで、この白濁液に生体溶解性無機繊維９６．２質量％を添加し、スラリー濃度が３質量％となるまで更に水を加え、生体溶解性無機繊維が均一に分散するまで攪拌した。得られたスラリーを孔径０．４５μｍの濾紙（「ＤＩＳＭＩＣ−２５ｃｓ」；ＡＤＶＡＮＴＥＣ社製）で濾過して、濾紙上に固形物を得た。固形物は組成分析の結果、無機繊維の表面にトリポリリン酸アルミニウムが被覆されたものであった。また、トリポリリン酸アルミニウムが被覆された生体溶解性無機繊維の写真を図１に示し、トリポリリン酸アルミニウムによる被覆処理をする前の生体溶解性無機繊維の写真を図２に示すが、図１の写真から、明らかに生体溶解性無機繊維の表面が被覆されていることが判る。このトリポリリン酸アルミニウムが被覆された生体溶解性無機繊維（以下、試料１ａとも記載する。）及び被覆処理をする前の生体溶解性繊維（以下試料２ａとも記載する。）を前述の生理食塩水溶解率及び蒸留水溶解率の測定方法により、４０℃における生理食塩水溶解率及び蒸留水溶解率を求めた。その結果を表２に示す。
(Reference example)
At room temperature, 2.3% by mass of aluminum dihydrogen tripolyphosphate, 1.3% by mass of silicon oxide and 0.2% by mass of magnesium oxide mixed in advance were added to water as a coating layer forming agent and stirred to obtain a cloudy liquid. . Next, 96.2% by mass of the biosoluble inorganic fiber was added to this cloudy liquid, and water was further added until the slurry concentration became 3% by mass, followed by stirring until the biosoluble inorganic fiber was uniformly dispersed. The obtained slurry was filtered through a filter paper having a pore size of 0.45 μm (“DISMIC-25cs”; manufactured by ADVANTEC) to obtain a solid on the filter paper. As a result of the compositional analysis, the solid material was one in which the surface of the inorganic fiber was coated with aluminum tripolyphosphate. In addition, a photograph of the biosoluble inorganic fiber coated with aluminum tripolyphosphate is shown in FIG. 1, and a photograph of the biosoluble inorganic fiber before being coated with aluminum tripolyphosphate is shown in FIG. This clearly shows that the surface of the biosoluble inorganic fiber is coated. This biosoluble inorganic fiber coated with aluminum tripolyphosphate (hereinafter also referred to as sample 1a) and the biosoluble fiber before coating (hereinafter also referred to as sample 2a) were dissolved in the aforementioned physiological saline. The physiological saline dissolution rate and the distilled water dissolution rate at 40 ° C. were determined by the method for measuring the rate and the distilled water dissolution rate. The results are shown in Table 2.
参考例の結果から、本発明の無機繊維質成形体に含有されている被覆層形成無機繊維（ａ）は、例え施工時等の作業時に、粉塵となって空気中に飛散し、作業者が該粉塵を吸入しても体内で溶解されやすい。 From the result of the reference example, the coating layer forming inorganic fiber (a) contained in the inorganic fiber molded body of the present invention is scattered in the air as dust during work such as construction, and the operator Even if the dust is inhaled, it is easily dissolved in the body.
本発明によれば、生体溶解性を有する無機繊維を用いる無機繊維質成形体であって、保管中に劣化し難くい無機繊維質成形体及び製造時に該無機繊維が劣化し難い無機繊維質成形体の製造方法を提供することができる。 According to the present invention, an inorganic fiber molded body that uses inorganic fibers having biosolubility, an inorganic fiber molded body that does not easily deteriorate during storage, and an inorganic fiber molded body that does not easily deteriorate during manufacture. A method of manufacturing a body can be provided.
Claims (3)
該被覆層形成無機繊維（ａ）の４０℃における生理食塩水溶解率が１％以上であり、
該被覆層形成無機繊維（ａ）が、無機繊維（ｂ）の表面に被覆層が形成されている繊維であり、
該無機繊維（ｂ）が、ＳｉＯ ２ ７５〜８０質量％、ＣａＯ＋ＭｇＯ １９〜２５質量％、Ａｌ ２ Ｏ ３ １〜３質量％を含む無機繊維であり、
該被覆層が、リン酸塩で形成されていること、
を特徴とする無機繊維質成形体。 Containing a coating layer forming inorganic fiber (a) and a binder,
Saline dissolution rate in the 40 ° C. of the coating layer forming the inorganic fiber (a) is Ri der 1% or more,
The coating layer-forming inorganic fiber (a) is a fiber having a coating layer formed on the surface of the inorganic fiber (b),
The inorganic fiber (b) is an inorganic fiber containing 75 to 80% by mass of SiO 2 , 19 to 25% by mass of CaO + MgO, and 1 to 3% by mass of Al 2 O 3 ,
The coating layer is formed of phosphate;
An inorganic fibrous shaped article characterized by
該無機繊維（ｂ）が、ＳｉＯ ２ ７５〜８０質量％、ＣａＯ＋ＭｇＯ １９〜２５質量％、Ａｌ ２ Ｏ ３ １〜３質量％を含む無機繊維であり、
該被覆層形成剤が、リン酸塩であること、
を特徴とする無機繊維質成形体の製造方法。 A slurry containing a coating layer-forming inorganic fiber (a) by mixing a coating layer-forming agent with a solvent, and then mixing an inorganic fiber (b) having a physiological saline solubility at 40 ° C. of 1% or more and a binder. slurry preparation step of obtaining a, and the solvent in the slurry, is filtered off with suction, it has a dehydration molding to obtain an inorganic fibrous molded body,
The inorganic fiber (b) is an inorganic fiber containing 75 to 80% by mass of SiO 2 , 19 to 25% by mass of CaO + MgO, and 1 to 3% by mass of Al 2 O 3 ,
The coating layer forming agent is a phosphate;
A method for producing an inorganic fibrous shaped article characterized by the above.
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| JPS61209940A (en) * | 1985-03-12 | 1986-09-18 | 旭硝子株式会社 | Fiber for reinforcement |
| JPH0474636B2 (en) * | 1983-08-26 | 1992-11-26 | ||
| JPH06306649A (en) * | 1993-04-16 | 1994-11-01 | Teika Corp | Pigment for preventive filiform corrosion |
| JP2005281079A (en) * | 2004-03-30 | 2005-10-13 | Nichias Corp | Indeterminate heat insulating material composition |
| JP2007197264A (en) * | 2006-01-27 | 2007-08-09 | Nichias Corp | Inorganic fiber molding |
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| JPS61209940A (en) * | 1985-03-12 | 1986-09-18 | 旭硝子株式会社 | Fiber for reinforcement |
| JPH06306649A (en) * | 1993-04-16 | 1994-11-01 | Teika Corp | Pigment for preventive filiform corrosion |
| JP2005281079A (en) * | 2004-03-30 | 2005-10-13 | Nichias Corp | Indeterminate heat insulating material composition |
| JP2007197264A (en) * | 2006-01-27 | 2007-08-09 | Nichias Corp | Inorganic fiber molding |
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