KR102708866B1 - A flame retardant coating composition prepared by the sol-gel method and a preparation method thereof - Google Patents
A flame retardant coating composition prepared by the sol-gel method and a preparation method thereof Download PDFInfo
- Publication number
- KR102708866B1 KR102708866B1 KR1020230106880A KR20230106880A KR102708866B1 KR 102708866 B1 KR102708866 B1 KR 102708866B1 KR 1020230106880 A KR1020230106880 A KR 1020230106880A KR 20230106880 A KR20230106880 A KR 20230106880A KR 102708866 B1 KR102708866 B1 KR 102708866B1
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- South Korea
- Prior art keywords
- flame retardant
- phosphate
- coating composition
- polysilanol
- retardant coating
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 93
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000008199 coating composition Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title description 2
- 238000003980 solgel method Methods 0.000 title description 2
- 239000000919 ceramic Substances 0.000 claims abstract description 53
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 46
- 239000010452 phosphate Substances 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 32
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000077 silane Inorganic materials 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 claims description 3
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- DLHTWZBWWPZUSD-UHFFFAOYSA-N aluminum nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3] DLHTWZBWWPZUSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 42
- 239000000463 material Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 231100000820 toxicity test Toxicity 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000005856 abnormality Effects 0.000 description 3
- 239000012795 eco-friendly flame retardant Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 241000699670 Mus sp. Species 0.000 description 2
- 230000003542 behavioural effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BDLVNNJRAIUIMO-UHFFFAOYSA-N amino(hydroxy)silicon Chemical compound N[Si]O BDLVNNJRAIUIMO-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- -1 metal hydroxide compound Chemical class 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001373 regressive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/80—Processes for incorporating ingredients
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 알루미노 실리케이트, 실란, 암모늄 아미노 폴리 실라놀 인산염 및 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말을 포함하는 것을 특징으로 하는 난연성 코팅제 조성물에 있어서, 상기 난연성 코팅제 조성물은 조성물 총 중량을 기준으로 상기 알루미노 실리케이트 20 내지 50 중량%, 상기 실란 10 내지 30 중량%, 상기 암모늄 아미노 폴리 실라놀 인산염 20 내지 50 중량% 및 상기 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말 2 내지 5중량%를 포함하는 것을 특징으로 한다.The present invention relates to a flame retardant coating composition comprising an aluminosilicate, a silane, an ammonium amino polysilanol phosphate, and a ceramic powder treated with the ammonium amino polysilanol phosphate, wherein the flame retardant coating composition comprises 20 to 50 wt% of the aluminosilicate, 10 to 30 wt% of the silane, 20 to 50 wt% of the ammonium amino polysilanol phosphate, and 2 to 5 wt% of the ceramic powder treated with the ammonium amino polysilanol phosphate, based on the total weight of the composition.
Description
본 발명은 가연성 소재에 코팅되어 난연성 도막을 부여하는 난연성 코팅제 조성물 및 난연성 코팅제 제조 방법에 관한 것으로서, 보다 구체적으로, 인계 난연제가 정교히 세라믹 올리고머의 망상구조안에 결합되어, 친환경적이고, 뛰어난 난연성을 제공하는 난연성 코팅제 조성물 및 난연성 코팅제 제조 방법에 관한 것이다.The present invention relates to a flame-retardant coating composition that provides a flame-retardant film by coating a combustible material, and a method for producing a flame-retardant coating, and more specifically, to a flame-retardant coating composition that is environmentally friendly and provides excellent flame retardancy by precisely combining a phosphorus flame retardant into the network structure of a ceramic oligomer, and a method for producing a flame-retardant coating.
난연제는 건축, 조선, 전기전자 및 교통 분야 등 산업 전반에 널리 적용되는 소재로, 화재에 대한 안전기준을 강화하는 전 세계적인 추세에 따라 지속적으로 수요가 증가하고 있다.Flame retardants are widely used in a wide range of industries, including construction, shipbuilding, electrical and electronics, and transportation, and their demand is continuously increasing in line with the global trend of strengthening fire safety standards.
또한, 최근 난연제는 시대적 변화와 요구에 따라, 단순한 화재 안정성 규제 뿐 아니라, 난연 재료의 친환경적 활용과 독성에 관한 안정성에도 그 중요성이 중시되어 가고 있다. In addition, in recent times, flame retardants are increasingly being given importance not only to simple fire safety regulations, but also to the eco-friendly use of flame retardant materials and stability regarding toxicity, in accordance with changes in the times and demands.
현재 산업적으로 주로 적용되는 난연 재료로는 비(非) 친환경성 재료가 많은데, 대표적인 예로는 할로겐계 난연제로, 할로겐계 난연제는 고온 가공 및 연소 시 주변 장비를 부식시키는 강한 산성 물질을 다량 생성할 뿐만 아니라 산소가 희박한 조건에서 연소될 경우 인체에 매우 해로운 발암물질인 할로겐화 다이옥신을 생성하는 등 환경 및 안전상에 심각한 문제점을 야기하는 것으로 알려져 전세계적으로 사용이 점차 제한되는 추세이다.Currently, many flame retardant materials mainly applied industrially are non-environmentally friendly materials. A representative example is halogenated flame retardants. Halogenated flame retardants not only produce large amounts of strong acidic substances that corrode surrounding equipment during high-temperature processing and combustion, but also produce halogenated dioxins, which are carcinogens that are very harmful to the human body when burned under conditions of low oxygen, and are known to cause serious environmental and safety problems. As such, their use is gradually being restricted worldwide.
이를 대체하기 위한 친환경성 난연제로는 인계 난연제나, 질소계 또는 금속수산화물계 등을 사용하고 있으나, 상기 친환경성 난연제는 내수성 및 내후성 등에 매우 취약하고, 코팅제로 활용되기 위해선 이에 적합한 바인더를 개발하여 혼합해야 하는 문제점과 더불어, 코팅제의 난연 퍼포먼스를 극대화하기 위한 연구 개발이 대두되고 있는 실정이다.To replace this, eco-friendly flame retardants such as phosphorus flame retardants, nitrogen-based flame retardants, or metal hydroxide-based flame retardants are being used. However, the eco-friendly flame retardants are very vulnerable to water resistance and weather resistance, and in order to be used as a coating agent, a suitable binder must be developed and mixed. In addition, research and development is being conducted to maximize the flame retardant performance of the coating agent.
본 발명이 해결하고자 하는 과제는, 난연 성능이 우수할 뿐만 아니라, 안전하고, 친환경적이며, 내수성 및 내후성 문제들이 해결된 친환경 난연성 코팅 원료에 대한 기술을 제공하고자 한다.The problem to be solved by the present invention is to provide a technology for an eco-friendly flame retardant coating raw material that not only has excellent flame retardancy performance, but is also safe, environmentally friendly, and has solved water resistance and weather resistance problems.
본 발명의 일 실시예에 따른 난연성 코팅제 조성물은 알루미노 실리케이트, 실란, 암모늄 아미노 폴리 실라놀 인산염 및 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말을 포함하는 것을 특징으로 한다.A flame retardant coating composition according to one embodiment of the present invention is characterized by including aluminosilicate, silane, ammonium amino polysilanol phosphate, and ceramic powder treated with ammonium amino polysilanol phosphate.
또한, 상기 난연성 코팅제 조성물은 조성물 총 중량을 기준으로 상기 알루미노 실리케이트 20 내지 50 중량%, 상기 실란 10 내지 30 중량%, 상기 암모늄 아미노 폴리 실라놀 인산염 20 내지 50 중량% 및 상기 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말 2 내지 5중량%를 포함하는 것을 특징으로 한다.In addition, the flame retardant coating composition is characterized by comprising 20 to 50 wt% of the aluminosilicate, 10 to 30 wt% of the silane, 20 to 50 wt% of the ammonium amino polysilanol phosphate, and 2 to 5 wt% of the ceramic powder treated with the ammonium amino polysilanol phosphate, based on the total weight of the composition.
또한, 상기 실란은 알콕시 타입의 테트라에톡시실란(Tetraethoxysilane), 메틸트리메톡시실란(Methyltrimethoxysilane), 비닐 타입의 비닐트리에톡시실란(Vinyltriethoxysilane), 비닐트리메톡시실란(Vinyltrimethoxysilane), 아미노 타입의 3-아미노프로필트리에톡시실란(3-Aminopropyltriethoxysilane), 3-아미노프로필트리메톡시실란(3-Aminopropyltrimethoxysilane) 에폭시 타입의 글리사이톡시프로필 메틸디메톡시실란(3-Glycidoxypropyl methyldimethoxysilane), 메타크릴 타입의 메타크릴옥시프로필 메틸 디메톡시실란(3-Methacryloxypropyl methyldimethoxysilane), 메타크릴옥시프로필 트리에톡시실란(3-Methacryloxypropyl triethoxysilane) 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나 이상인 것을 특징으로 한다.In addition, the silane is characterized by being at least one selected from the group consisting of alkoxy type tetraethoxysilane, methyltrimethoxysilane, vinyl type vinyltriethoxysilane, vinyltrimethoxysilane, amino type 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, epoxy type 3-glycidoxypropyl methyldimethoxysilane, methacryl type 3-methacryloxypropyl methyldimethoxysilane, methacryloxypropyl triethoxysilane, and combinations thereof.
또한, 상기 암모늄 아미노 폴리 실라놀 인산염은 3-아미노프로필트리에톡시실란(3-Aminopropyl triethoxysilane)과 암모니아수가 첨가된 액상에 알카리형 실리카졸(sol)을 혼합 후, 산성 타입의 실리카졸(sol)과 혼합된 인산을 반응시켜 얻어낸 염(salt)을 인계 난연제에 습식 코팅 처리 및 건조하여 생성된 물질인 것을 특징으로 한다. 또한, 상기 인계 난연제는 암모늄 폴리 포스페이트, 크레실 디페닐 포스페이트, 트리크레실 포스페이트, 트리크실릴 포스페이트, 트리페닐 포스페이트, 레졸시놀 비스(디페닐 포스페이트) 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나 이상인 것을 특징으로 한다.In addition, the ammonium amino polysilanol phosphate is characterized in that it is a material produced by mixing an alkaline silica sol in a liquid phase to which 3-aminopropyl triethoxysilane and ammonia water are added, reacting phosphoric acid mixed with an acidic silica sol, obtaining a salt, wet coating the obtained salt on a phosphorus flame retardant, and drying the same. In addition, the phosphorus flame retardant is characterized in that at least one selected from the group consisting of ammonium polyphosphate, cresyl diphenyl phosphate, tricresyl phosphate, tricylyl phosphate, triphenyl phosphate, resorcinol bis(diphenyl phosphate), and combinations thereof.
상기 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말은 담체 세라믹 분말 표면이 상기 암모늄 아미노 폴리 실라놀 인산염으로 습식 표면 처리되는 것을 특징으로 한다. 또한, 상기 암모늄 아미노 폴리 실라놀 인산염과 상기 담체 세라믹 분말의 중량비는 4:6 인 것을 특징으로 한다. 또한, 상기 담체 세라믹 분말는 마이카, 수산화마그네슘, 알루미늄, 알루미나, 아나타제 티탄 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나 이상인 것을 특징으로 한다.The above-mentioned ammonium amino polysilanol phosphate-treated ceramic powder is characterized in that the surface of the carrier ceramic powder is wet-surface-treated with the ammonium amino polysilanol phosphate. In addition, the weight ratio of the ammonium amino polysilanol phosphate and the carrier ceramic powder is characterized in that it is 4:6. In addition, the carrier ceramic powder is characterized in that it is at least one selected from the group consisting of mica, magnesium hydroxide, aluminum, alumina, anatase titanium, and combinations thereof.
또한, 상기 난연성 코팅제 조성물은 조성물 총 중량을 기준으로 유기수지 1 내지 10 중량%를 더 포함하는 것을 특징으로 한다.In addition, the flame retardant coating composition is characterized in that it further contains 1 to 10 wt% of organic resin based on the total weight of the composition.
또한, 상기 유기수지는 아크릴 수지, 에폭시 수지, 우레탄 수지 및 이들의 화합물로 이루어진 군으로부터 선택된 적어도 하나 이상인 것을 특징으로 한다.In addition, the organic resin is characterized by being at least one selected from the group consisting of acrylic resin, epoxy resin, urethane resin, and compounds thereof.
한편, 본 발명의 일 실시예에 따른 난연성 코팅제 조성물의 제조 방법은 (a) 실리콘 옥사이드 졸(Sol)과 알루미늄9수화물을 합성하여 알루미노 실리케이트가 제조되는 단계; (b) 상기 알루미노 실리케이트에 실란을 투입하여 나노망상구조의 세라믹 올리고머가 제조되는 단계; (c) 상기 세라믹 올리고머에 암모늄 아미노 폴리 실라놀 인산염을 투입하여 난연성 세라믹 올리고머 코팅제가 제조되는 단계; 및 (d) 상기 난연성 세라믹 올리고머 코팅제에 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말을 투입하여 난연성 코팅제 조성물이 제조되는 단계;를 포함하는 것을 특징으로 한다. 또한, (e) 상기 난연성 코팅제 조성물에 유기수지가 투입되는 단계;를 더 포함하는 것을 특징으로 한다.Meanwhile, a method for producing a flame-retardant coating composition according to an embodiment of the present invention is characterized by including the steps of (a) synthesizing silicon oxide sol and aluminum non-hydrate to produce an aluminosilicate; (b) adding silane to the aluminosilicate to produce a ceramic oligomer having a nano-network structure; (c) adding ammonium amino polysilanol phosphate to the ceramic oligomer to produce a flame-retardant ceramic oligomer coating agent; and (d) adding ceramic powder treated with ammonium amino polysilanol phosphate to the flame-retardant ceramic oligomer coating agent to produce a flame-retardant coating composition. In addition, the method is characterized by further including the step of (e) adding an organic resin to the flame-retardant coating composition.
본 발명에 따른 난연성 코팅제 조성물 및 난연성 코팅제 조성물 제조 방법은 친환경적인 난연제를 수득할 수 있다.The flame retardant coating composition and the method for producing the flame retardant coating composition according to the present invention can obtain an environmentally friendly flame retardant.
또한, 가연성 소재에 코팅되어 난연성 도막을 부여할 시, 여러 가지 케미칼 인자로부터 안전하고, 내수성 및 내후성 문제들로부터 강건할 수 있다.In addition, when coated on a combustible material to provide a flame retardant coating, it can be safe from various chemical factors and robust from water resistance and weather resistance problems.
또한, 합성 차원에서 처리된 나노 망상구조 수준의 바인더와 분말들은 일괄적인 코팅 배열에 도움을 줄 수 있어서, 면 섬유 재질에 코팅하게 되면 밀착성 및 부착성이 우수하고, 도막의 불연 특징의 원료와 난연 특징의 원료들이 밀도 있게 분산되어 있어서 매우 효과 높은 난연특성을 얻을 수 있다.In addition, the binder and powders at the nano-network level processed at the synthetic level can help in uniform coating arrangement, so that when coated on cotton fiber material, the adhesion and bonding are excellent, and the raw materials with non-flammable properties and raw materials with flame retardant properties of the coating are densely dispersed, so that highly effective flame retardant properties can be obtained.
다만, 본 발명의 효과가 상술한 효과들로 제한되는 것은 아니며, 언급되지 아니한 효과들은 본 명세서로부터 본 발명이 속하는 기술분야에서 통상의 지식을 가진자에게 명확히 이해될 수 있을 것이다.However, the effects of the present invention are not limited to the effects described above, and effects not mentioned can be clearly understood by a person having ordinary skill in the art to which the present invention belongs from this specification.
도 1 및 2는 본 발명의 일 실시예에 따른 난연성 코팅제 조성물로 코팅된 시편의 열 방출률 시험을 도시한 도면이다.
도 3 및 도 4는 본 발명의 일 실시예에 따른 난연성 코팅제 조성물로 코팅된 시편의 가스유해성 시험을 도시한 도면이다.
도 5는 본 발명의 일 실시예에 따른 난연성 코팅제 조성물로 코팅된 시편의 추가 열적 시험을 도시한 도면이다.
도 6은 본 발명의 일 실시예에 따른 난연성 코팅제 조성물로 코팅된 시편의 전기적 특성 시험을 도시한 도면이다.FIGS. 1 and 2 are drawings illustrating a heat release rate test of a specimen coated with a flame retardant coating composition according to one embodiment of the present invention.
FIGS. 3 and 4 are drawings illustrating a gas toxicity test of a specimen coated with a flame retardant coating composition according to one embodiment of the present invention.
FIG. 5 is a drawing illustrating additional thermal testing of a specimen coated with a flame retardant coating composition according to one embodiment of the present invention.
FIG. 6 is a drawing illustrating an electrical characteristic test of a specimen coated with a flame retardant coating composition according to one embodiment of the present invention.
이하에서는 본 발명의 구체적인 실시예를 상세하게 설명한다. 다만, 본 발명의 사상은 제시되는 실시예에 제한되지 아니하고, 본 발명의 사상을 이해하는 당업자는 동일한 사상의 범위 내에서 다른 구성요소를 추가, 변경, 삭제 등을 통하여, 퇴보적인 다른 발명이나 본 발명 사상의 범위 내에 포함되는 다른 실시예를 용이하게 제안할 수 있을 것이나, 이 또한 본원 발명 사상 범위 내에 포함된다고 할 것이다.Hereinafter, specific embodiments of the present invention will be described in detail. However, the idea of the present invention is not limited to the presented embodiments, and those skilled in the art who understand the idea of the present invention will be able to easily propose other regressive inventions or other embodiments included within the scope of the idea of the present invention by adding, changing, deleting, etc. other components within the scope of the same idea, but this will also be considered to be included within the scope of the idea of the present invention.
또한, 본 발명의 다양한 실시예는 서로 다르지만 상호 배타적일 필요는 없음이 이해되어야 한다. 일례로, 여기에 기재되어 있는 특정 형상, 구조 및 특성은 일 실시예에 관련하여 본 발명의 정신 및 범위를 벗어나지 않으면서 다른 실시예로 구현될 수 있다. 또한, 각각의 개시된 실시예 내의 개별 구성요소의 위치 또는 배치는 본 발명의 정신 및 범위를 벗어나지 않으면서 변경될 수 있음이 이해되어야 한다. 따라서, 후술하는 상세한 설명은 한정적인 의미로서 취하려는 것이 아니며, 본 발명의 범위는, 적절하게 설명된다면, 그 청구항들이 주장하는 것과 균등한 모든 범위와 더불어 첨부된 청구항에 의해서만 한정된다.It should also be understood that the various embodiments of the present invention, while different, are not necessarily mutually exclusive. For example, specific shapes, structures, and characteristics described herein may be implemented in other embodiments without departing from the spirit and scope of the present invention with respect to one embodiment. It should also be understood that the positions or arrangements of individual components within each disclosed embodiment may be changed without departing from the spirit and scope of the present invention. Accordingly, the following detailed description is not intended to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims, along with the full scope of equivalents to which such claims are entitled, if properly so described.
덧붙여, 본 발명에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 발명의 명세서 전체에서 어떤 구성요소를 '포함'한다는 것은 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있다는 것을 의미한다.In addition, the terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. Throughout the specification of the present invention, the term "including" a certain component does not exclude other components, but rather means that other components may be included, unless specifically stated otherwise.
이하, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 본 발명을 용이하게 실시할 수 있도록 하기 위하여, 본 발명의 바람직한 실시예들에 관하여 상세히 설명하기로 한다.Hereinafter, preferred embodiments of the present invention will be described in detail so that a person having ordinary skill in the art to which the present invention pertains can easily practice the present invention.
본 발명에서 난연제라 함은 연소하기 쉬운 성질을 가진 고분자 재료나 섬유 가연성 물질에 난연성 세라믹 올리고머, 인산염, 질소화합물, 그리고 수산화 금속화합물 및 난연 표면 처리된 세라믹 분말 등의 난연성 부여 효과가 큰 화합물을 첨가함으로써 발화를 늦춰주고, 연소의 확대를 막아주는 물질을 의미한다. 본 발명에서는 열적 및 기계적 물성이 우수하고 친환경적인 난연성 코팅제 조성물을 제공하고자 한다.In the present invention, the flame retardant refers to a material that delays ignition and prevents the spread of combustion by adding a compound having a high flame retardancy effect, such as a flame retardant ceramic oligomer, phosphate, nitrogen compound, metal hydroxide compound, and flame retardant surface-treated ceramic powder, to a polymer material or fiber flammable material that is prone to combustion. The present invention seeks to provide an environmentally friendly flame retardant coating composition with excellent thermal and mechanical properties.
이러한 효과를 제공하기 위하여, 본 발명의 일 실시예에 따른 난연성 코팅제 조성물은 알루미노 실리케이트, 실란, 암모늄 아미노 폴리 실라놀 인산염 및 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말을 포함할 수 있다. 또한, 상기 난연성 코팅제 조성물은 조성물 총 중량을 기준으로 상기 알루미노 실리케이트 20 내지 50 중량%, 상기 실란 10 내지 30 중량%, 상기 암모늄 아미노 폴리 실라놀 인산염 20 내지 50 중량% 및 상기 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말 2 내지 5중량%를 포함하는 것을 특징으로 한다.In order to provide such effects, a flame retardant coating composition according to one embodiment of the present invention may include an aluminosilicate, a silane, an ammonium amino polysilanol phosphate, and a ceramic powder treated with the ammonium amino polysilanol phosphate. In addition, the flame retardant coating composition is characterized in that it includes 20 to 50 wt% of the aluminosilicate, 10 to 30 wt% of the silane, 20 to 50 wt% of the ammonium amino polysilanol phosphate, and 2 to 5 wt% of the ceramic powder treated with the ammonium amino polysilanol phosphate, based on the total weight of the composition.
상기 알루미노 실리케이트의 경우 바인더 역할을 수행할 수 있다. 상기 알루미노 실리케이트는 알루미나와 실리카가 결합한 구조로서, 일반적으로 알루미늄 원소에 대하여 실리콘 원소의 개수가 1 내지 5개인 구조이다. 상기 알루미노 실리케이트는 기본적으로 입자의 표면 특성이 다른 재료와 달리 매우 다양하여, 바인더의 역할을 수행할 수 있으며, 자연적으로 안정성이 높으며, 고온에서 안정적인 물질이기 때문에 내후성, 내화성 및 내열성이 우수한 특성이 있다. 본 발명에서는 조성물 총 중량을 기준으로 알루미노 실리케이트를 20 내지 50중량%를 포함할 수 있으며, 20중량% 미만일 경우, 바인더의 역할을 제대로 수행할 수 없으며, 50중량%를 초과할 경우, 상대적으로 다른 재료의 혼합비가 낮아져, 우수한 난연 퍼포먼스를 수행하기 어려울 수 있다.The above aluminosilicate can act as a binder. The above aluminosilicate is a structure in which alumina and silica are combined, and generally has a structure in which the number of silicon elements is 1 to 5 for aluminum elements. The above aluminosilicate basically has surface characteristics of particles that are very diverse compared to other materials, and can act as a binder. It is naturally stable and is a stable material at high temperatures, so it has excellent properties such as weather resistance, fire resistance, and heat resistance. In the present invention, the aluminosilicate may be included in an amount of 20 to 50 wt% based on the total weight of the composition. When it is less than 20 wt%, the role of a binder cannot be properly performed, and when it exceeds 50 wt%, the mixing ratio of other materials becomes relatively low, making it difficult to perform excellent flame retardant performance.
또한, 본 발명에서 투입되는 상기 알루미노 실리케이트는 Sol 형태일 수 있으며, 고형분이 30 내지 40%인 것일 수 있다. 이때, 상기 알루미노 실리케이트는 실리콘 옥사이드 Sol(고형분 30%) 및 질산알루미늄9수화물을 3:7 내지 7:3 중량비로 투입하고 60℃온도로 4시간 동안 합성을 통해 제조될 수 있다.In addition, the aluminosilicate introduced in the present invention may be in the form of Sol and may have a solid content of 30 to 40%. At this time, the aluminosilicate may be manufactured by introducing silicon oxide Sol (solid content of 30%) and aluminum nitrate nonahydrate in a weight ratio of 3:7 to 7:3 and synthesizing at a temperature of 60°C for 4 hours.
또한, 본 발명에서 제공되는 실란은 알콕시 타입의 테트라에톡시실란(Tetraethoxysilane), 메틸트리메톡시실란(Methyltrimethoxysilane), 비닐 타입의 비닐트리에톡시실란(Vinyltriethoxysilane), 비닐트리메톡시실란(Vinyltrimethoxysilane), 아미노 타입의 3-아미노프로필트리에톡시실란(3-Aminopropyltriethoxysilane), 3-아미노프로필트리메톡시실란(3-Aminopropyltrimethoxysilane) 에폭시 타입의 글리사이톡시프로필 메틸디메톡시실란(3-Glycidoxypropyl methyldimethoxysilane), 메타크릴 타입의 메타크릴옥시프로필 메틸 디메톡시실란(3-Methacryloxypropyl methyldimethoxysilane), 메타크릴옥시프로필 트리에톡시실란(3-Methacryloxypropyl triethoxysilane) 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나 이상일 수 있으며, 바람직하게는 테트라에톡시실란, 비닐트리에톡시실란 및 3-아미노프로필트리에톡시실란이 모두 포함될 수 있으며, 그 비율은 1:1:1일 수 있으나, 이에 한정하지는 않는다. 이와 같이, 본 발명은 할로겐 화합물 등의 유해화합물 난연제 등을 대체하여 여러 작용기가 있는 친환경적인 실란(silane)을 활용하여 기존 성능을 향상시킨 유-무기 하이브리드 졸을 합성할 수 있다. 또한, 실란을 한 종류가 아닌 복수의 종류를 채택하여 혼합함으로써, 물성을 개선시킬 수 있다.In addition, the silane provided in the present invention may be at least one selected from the group consisting of alkoxy type tetraethoxysilane, methyltrimethoxysilane, vinyl type vinyltriethoxysilane, vinyltrimethoxysilane, amino type 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, epoxy type 3-glycidoxypropyl methyldimethoxysilane, methacryl type 3-methacryloxypropyl methyldimethoxysilane, methacryloxypropyl triethoxysilane, and combinations thereof. , and preferably, tetraethoxysilane, vinyltriethoxysilane and 3-aminopropyltriethoxysilane can all be included, and the ratio can be 1:1:1, but is not limited thereto. In this way, the present invention can synthesize an organic-inorganic hybrid sol with improved performance by utilizing an environmentally friendly silane having various functional groups to replace hazardous compounds such as halogen compounds and flame retardants. In addition, by adopting and mixing multiple types of silanes rather than one type, the physical properties can be improved.
여기서, 실란은 상기 알루미노 실리케이트와 반응하여, 가수분해 및 중축합 반응을 진행시키는 졸-겔 법에 의해 나노망상구조의 세라믹 올리고머를 제조할 수 있다. 이때, 상기 알루미노 실리케이트와 상기 실란의 급격한 반응을 제어하고자, 쿨링 자켓 반응기에서 10℃미만의 온도로 4시간 동안 반응시키어 내열성을 갖춘 나노망상구조의 세라믹 올리고머를 제조하였다. 이는, 후술될 인계 난연제가 나노망상구조 안에서 정교히 결합되기 위함이며, 상기 쿨링 자켓 반응기에서 온도와 시간, 압력 등 물리적인 변수의 조절을 통해 세라믹 올리고머의 나노망상구조 설계를 완성하였다. 일례로, 반응 시 온도가 급격히 상승하는 현상은 세라믹 올리고머를 중축합시켜 겔레이션(Gelation) 되게 하는 원인이 될 수 있기 때문에, 반응 온도가 30℃이상 올라가지 않도록 쿨링 자켓 반응기에서 제어해야 한다.Here, silane can be reacted with the aluminosilicate to produce a ceramic oligomer having a nano-network structure by a sol-gel method in which hydrolysis and condensation reactions occur. At this time, in order to control the rapid reaction of the aluminosilicate and the silane, the reaction was performed at a temperature of less than 10°C for 4 hours in a cooling jacket reactor to produce a ceramic oligomer having a nano-network structure with heat resistance. This is to ensure that the phosphorus flame retardant, which will be described later, is precisely combined within the nano-network structure, and the design of the nano-network structure of the ceramic oligomer was completed by controlling physical variables such as temperature, time, and pressure in the cooling jacket reactor. For example, since a phenomenon in which the temperature rises rapidly during the reaction can cause the ceramic oligomer to condense and gelate, the reaction temperature should be controlled so as not to rise above 30°C in the cooling jacket reactor.
또한, 본 발명에서 제공되는 상기 암모늄 아미노 폴리 실라놀 인산염은 3-아미노프로필트리에톡시실란(3-Aminopropyl triethoxysilane)과 암모니아수가 첨가된 액상에 알카리형 실리카졸(sol)을 혼합 후, 산성 타입의 실리카졸(sol)과 혼합된 인산을 반응시켜 얻어낸 염(salt)을 인계 난연제에 습식 코팅 처리 및 건조 처리하여 생성된 물질이며, 상기 인계 난연제는 암모늄 폴리 포스페이트, 크레실 디페닐 포스페이트, 트리크레실 포스페이트, 트리크실릴 포스페이트, 트리페닐 포스페이트, 레졸시놀 비스(디페닐 포스페이트) 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나 이상인 것을 특징으로 한다. In addition, the ammonium amino polysilanol phosphate provided in the present invention is a material produced by mixing an alkaline silica sol in a liquid phase to which 3-aminopropyl triethoxysilane and ammonia water are added, reacting phosphoric acid mixed with an acidic silica sol, and then wet coating and drying the obtained salt on a phosphorus flame retardant, and the phosphorus flame retardant is characterized in that at least one selected from the group consisting of ammonium polyphosphate, cresyl diphenyl phosphate, tricresyl phosphate, tricylyl phosphate, triphenyl phosphate, resorcinol bis(diphenyl phosphate), and combinations thereof.
또한, 상기 아미노 실라놀 폴리인산이 결합된 인계 난연제는 연소과정에서 가연성물질과 반응해 고분자 표면에 견고한 탄화막(Carbonaceous Layer)을 형성하고, 이 탄화막은 연소에 필요한 산소를 차단하여 난연효과를 제공한다. 특히 인계 난연제는 고분자 내의 산소원소와 반응하여 탈수, 탄화함으로써 난연 효과를 발휘하기 때문에 산소 원소를 함유한 고분자에서 효과적으로 난연 역할을 수행할 수 있다.In addition, the phosphorus flame retardant combined with the amino silanol polyphosphate reacts with a combustible substance during the combustion process to form a solid carbonaceous layer on the surface of the polymer, and this carbonaceous layer blocks the oxygen necessary for combustion, thereby providing a flame retardant effect. In particular, the phosphorus flame retardant exhibits a flame retardant effect by reacting with the oxygen element in the polymer to dehydrate and carbonize, so it can effectively perform a flame retardant role in polymers containing the oxygen element.
또한, 본 발명은 상기 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말을 더 투입하여 난연성을 극대화할 수 있다. 여기서, 상기 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말은 담체 세라믹 분말 표면이 상기 암모늄 아미노 폴리 실라놀 인산염으로 습식 표면 처리된 것으로, 상기 암모늄 아미노 폴리 실라놀 인산염과 상기 담체 세라믹 분말의 중량비는 4:6 인 것을 특징으로 한다. 이때, 상기 담체 세라믹 분말은 마이카, 수산화마그네슘, 알루미늄, 알루미나, 아나타제 티탄 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나 이상일 수 있으며, 상기 담체 세라믹 분말은 수산화마그네슘, 알루미늄 및 아나타제 티탄을 각각 1:2:1 비율로 혼합하는 것일 수 있다. 또한, 상기 담체 세라믹 분말은 직경이 100 내지 1000㎚인 것을 특징으로 한다. 상기와 같은 크기로 포함되는 경우, 우수한 분산효과를 통하여 도막의 밀도가 증가하는 것일 수 있다. 즉, 상기와 같이 증가된 도막의 밀도는 화염이 피도체에 닿는 시간을 줄이고 탄화막을 이룬 난연 성분의 성능을 더욱 단단하게 함으로써 난연성이 향상되는 것일 수 있다.In addition, the present invention can maximize flame retardancy by further adding the ceramic powder treated with the ammonium amino polysilanol phosphate. Here, the ceramic powder treated with the ammonium amino polysilanol phosphate is characterized in that the surface of the carrier ceramic powder is wet-surface-treated with the ammonium amino polysilanol phosphate, and the weight ratio of the ammonium amino polysilanol phosphate and the carrier ceramic powder is 4:6. At this time, the carrier ceramic powder may be at least one selected from the group consisting of mica, magnesium hydroxide, aluminum, alumina, anatase titanium, and combinations thereof, and the carrier ceramic powder may be a mixture of magnesium hydroxide, aluminum, and anatase titanium in a ratio of 1:2:1, respectively. In addition, the carrier ceramic powder is characterized in that it has a diameter of 100 to 1000 nm. When included in the above size, the density of the coating film may increase through an excellent dispersion effect. That is, the increased film density as described above may improve flame retardancy by reducing the time that the flame reaches the conductor and further strengthening the performance of the flame retardant component forming the carbon film.
또한, 본 발명은 상기 난연성 코팅제 조성물은 조성물 총 중량을 기준으로 유기수지 1 내지 10 중량%를 더 포함할 수 있으며, 바람직하게는 1 내지 5중량%를 포함할 수 있다. 이때, 상기 유기수지는 아크릴 수지, 에폭시 수지, 우레탄 수지 및 이들의 화합물로 이루어진 군으로부터 선택된 적어도 하나 이상인 것을 특징으로 하며, 본 발명은 상기 유기수지를 더 포함하여 난연성 코팅제 조성물의 부착성을 증대시킬 수 있다.In addition, the flame retardant coating composition of the present invention may further include 1 to 10 wt% of an organic resin based on the total weight of the composition, and preferably 1 to 5 wt%. At this time, the organic resin is characterized in that it is at least one selected from the group consisting of acrylic resin, epoxy resin, urethane resin, and compounds thereof, and the present invention can increase the adhesion of the flame retardant coating composition by further including the organic resin.
한편, 이하에서는 본 발명에 따른 난연성 코팅제 조성물의 제조 방법이 제공된다. 또한, 전술한 난연성 코팅제 조성물과 동일한 내용이 적용될 수 있고, 중복되는 범위 내에서 설명은 생략하도록 한다.Meanwhile, a method for producing a flame retardant coating composition according to the present invention is provided below. In addition, the same contents as the flame retardant coating composition described above can be applied, and the description is omitted within the overlapping scope.
본 발명에 따른 난연성 코팅제 조성물의 제조 방법은 (a) 실리콘 옥사이드 졸(Sol)과 알루미늄9수화물을 합성하여 알루미노 실리케이트가 제조되는 단계; (b) 상기 알루미노 실리케이트에 실란을 투입하여 나노망상구조의 세라믹 올리고머가 제조되는 단계; (c) 상기 세라믹 올리고머에 암모늄 아미노 폴리 실라놀 인산염을 투입하여 난연성 세라믹 올리고머 코팅제가 제조되는 단계; 및 (d) 상기 난연성 세라믹 올리고머 코팅제에 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말을 투입하여 난연성 코팅제 조성물이 제조되는 단계;를 포함하는 것을 특징으로 한다.The method for producing a flame-retardant coating composition according to the present invention is characterized by including: (a) a step of synthesizing silicon oxide sol and aluminum nonahydrate to produce an aluminosilicate; (b) a step of adding silane to the aluminosilicate to produce a ceramic oligomer having a nano-network structure; (c) a step of adding ammonium amino polysilanol phosphate to the ceramic oligomer to produce a flame-retardant ceramic oligomer coating agent; and (d) a step of adding ceramic powder treated with ammonium amino polysilanol phosphate to the flame-retardant ceramic oligomer coating agent to produce a flame-retardant coating composition.
또한, (e) 상기 난연성 코팅제 조성물에 유기수지가 투입되는 단계;를 더 포함하는 것을 특징으로 한다.In addition, it is characterized by further including a step of (e) adding an organic resin to the flame retardant coating composition.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실험예 및/또는 실시예에 대하여 상세히 설명한다. 그러나, 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실험예 및/또는 실시예에 한정되지 않는다.Hereinafter, experimental examples and/or embodiments of the present invention will be described in detail so that those with ordinary skill in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the experimental examples and/or embodiments described herein.
<실시예><Example>
난연성 코팅제 조성물의 제조Preparation of flame retardant coating composition
실리콘 옥사이드 Sol(고형분 30%) 및 질산알루미늄9수화물을 3:7 내지 7:3 중량비로 투입하고 60℃온도로 4시간 동안 합성을 통해 알루미노 실리케이트 Sol(고형분 30~40%)을 제조하였다.Aluminosilicate Sol (solid content 30-40%) was manufactured by adding silicon oxide Sol (solid content 30%) and aluminum nitrate nonahydrate in a weight ratio of 3:7 to 7:3 and synthesizing at 60°C for 4 hours.
다음으로, 제조된 상기 알루미노 실리케이트 Sol 40중량%에 실란 20중량%를 투입하고, 상기 알루미노 실리케이트와 상기 실란의 급격한 반응을 제어하고자, 쿨링 자켓 반응기에서 10℃미만의 온도로 4시간 동안 반응시키어 나노망상구조의 세라믹 올리고머를 제조하였다. 이때, 투입된 실란은 테트라에톡시실란, 비닐트리에톡시실란 및 3-아미노프로필트리에톡시실란을 1:1:1의 비율로 투입하였다.Next, 20 wt% of silane was added to 40 wt% of the manufactured aluminosilicate Sol, and in order to control the rapid reaction between the aluminosilicate and the silane, the reaction was performed in a cooling jacket reactor at a temperature of less than 10°C for 4 hours to manufacture a ceramic oligomer having a nano-network structure. At this time, the added silanes were tetraethoxysilane, vinyltriethoxysilane, and 3-aminopropyltriethoxysilane in a ratio of 1:1:1.
다음으로, 상기 세라믹 올리고머에 암모늄 아미노 폴리 실라놀 인산염 30중량%를 투입하고, 온도를 60 내지 70℃까지 상승시키고 2시간 동안 반응시키어 난연성 세라믹 올리고머 코팅제를 제조하였다.Next, 30 wt% of ammonium amino polysilanol phosphate was added to the ceramic oligomer, the temperature was raised to 60 to 70°C, and the reaction was performed for 2 hours to produce a flame-retardant ceramic oligomer coating agent.
이때, 상기 세라믹 올리고머 코팅제의 난연성을 극대화하기 위해 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말 5중량%을 투입 및 교반시켰다. 여기서, 상기 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말은 담체 세라믹 분말 표면이 상기 암모늄 아미노 폴리 실라놀 인산염으로 습식 표면 처리되는 것을 일컫는 것으로, 상기 암모늄 아미노 폴리 실라놀 인산염과 수산화 마그네슘, 알루미늄, 아나타제 티탄의 비가 1:2:1인 담체 세라믹 분말을 4:6의 중량비로 투입하여 혼합시키어, 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말을 제조하였다.At this time, in order to maximize the flame retardancy of the ceramic oligomer coating agent, 5 wt% of the ceramic powder treated with ammonium amino polysilanol phosphate was added and stirred. Here, the ceramic powder treated with ammonium amino polysilanol phosphate refers to a ceramic powder whose surface is wet-surface-treated with the ammonium amino polysilanol phosphate. The ammonium amino polysilanol phosphate and the carrier ceramic powder having a ratio of magnesium hydroxide, aluminum, and anatase titanium of 1:2:1 were added at a weight ratio of 4:6 and mixed to manufacture the ceramic powder treated with ammonium amino polysilanol phosphate.
마지막으로, 코팅제의 부착력을 증진시키기 위해 유기수지로 아크릴 수지 5중량%를 투입하였으며, 산성 타입의 유기수지를 선정하여 pH 농도에 의한 충돌이 발생되지 않도록 하여, 본 발명에 따른 난연성 코팅제 조성물을 제조하였다. Finally, in order to improve the adhesion of the coating agent, 5 wt% of acrylic resin was added as an organic resin, and an acidic type organic resin was selected to prevent a conflict due to pH concentration, thereby producing a flame retardant coating composition according to the present invention.
<실험예><Experimental example>
본 발명의 난연성 코팅제 조성물의 열 방출 및 가스유해성을 테스트하기 위해, 가연성 소재인 면 섬유를 상기 난연성 코팅제 조성물로 코팅하였으며, 이때, 코팅은 침적 코팅 및 Bar 코팅 방식으로 수행되었으며, 코팅 후 건조 온도 및 시간은 100 내지 150℃에서 30분 간 수행되었다.In order to test the heat release and gas toxicity of the flame retardant coating composition of the present invention, cotton fiber, which is a combustible material, was coated with the flame retardant coating composition. At this time, the coating was performed by immersion coating and bar coating, and the drying temperature and time after coating were 100 to 150°C for 30 minutes.
실험예 1. 열 방출 시험Experimental Example 1. Heat Release Test
실험예 1의 열 방출 시험에 관한 조건은 아래와 같다.The conditions for the heat release test of Experimental Example 1 are as follows.
① 열 방출 시험 조건① Heat release test conditions
- 가열면 : 앞, 뒷면 동일- Heating surface: Front and back are the same
- 시험 환경 : 온도 (21.0~25.0)℃, 상대습도 (48.0~52.0)% R.H- Test environment: Temperature (21.0~25.0)℃, relative humidity (48.0~52.0)% R.H.
- 시험 시간(min) : 10- Test time (min): 10
- 오리피스 상수 C(m1/2.g1/2.K1/2) : 0.036741- Orifice constant C(m 1/2 .g 1/2 .K 1/2 ) : 0.036741
- 복사열 (kW/M2) : 50±1- Radiant heat (kW/M 2 ): 50±1
- 배출장치유속 (m3/s) : 0.024 ± 0.002- Discharge device flow rate (m 3 /s): 0.024 ± 0.002
② 열 방출 시험 시편 조건② Heat release test specimen conditions
③ 시험 결과③ Test results
도 1을 참조하면, 상기 시편 1 내지 3의 실험 결과, 가열 개시 후 10분간 총 방출열량은 2MJ/㎡ 이하가 산출되었으며, 10분간 최대 열방출률이 10초 이상 연속으로 200kW/㎡ 를 초과하는 구간이 전혀 확인되지 않음을 알 수 있었다.Referring to Fig. 1, the experimental results of the above specimens 1 to 3 showed that the total heat release amount for 10 minutes after the start of heating was 2 MJ/㎡ or less, and it was found that there was no section in which the maximum heat release rate exceeded 200 kW/㎡ for 10 seconds or more continuously for 10 minutes.
또한, 도 2를 참조하면, 상기 시편을 10분간 가열 후 시험체를 관통하는 방화상 유해한 균열(시험체가 갈라져 바닥면이 보이는 변형을 말한다), 구멍(시험체 표면으로부터 바닥면이 보이는 변형을 말한다) 및 용융(시험체가 녹아서 바닥면이 보이는 경우를 말한다) 등이 없음을 확인할 수 있었으며, 시험체 두께의 20%를 초과하는 일부 용융 및 수축이 없음을 확인할 수 있었다.In addition, referring to FIG. 2, it was confirmed that there were no fire-hazardous cracks penetrating the test piece (referring to a deformation in which the test piece is split and the bottom surface is visible), holes (referring to a deformation in which the bottom surface is visible from the surface of the test piece), and melting (referring to a case in which the test piece melts and the bottom surface is visible) after heating the test piece for 10 minutes, and it was confirmed that there was no partial melting and shrinkage exceeding 20% of the test piece thickness.
따라서, 본 발명은 한국산업표준 KS F ISO 5660-1[연소성능시험-열 방출, 연기 발생, 질량 감소율-제1부 : 열 방출률(콘칼로리미터법)]에 따른 가열시험 결과, 건축자재등 품질인정 및 관리기준(국토교통부고시 제2023-24호)의 제24조 "준불연재료의 성능기준"을 충분히 만족하는 것을 확인할 수 있었으며, 본 발명의 난연성 코팅제 조성물은 난연재료의 성능을 뛰어넘어, 준불연재료의 성능에 준하는 난연성능을 수행할 수 있음을 확인할 수 있었다.Accordingly, the present invention was confirmed to sufficiently satisfy Article 24, "Performance standards for semi-non-combustible materials" of the Quality Recognition and Management Standards for Building Materials, etc. (Ministry of Land, Infrastructure and Transport Notice No. 2023-24), as a result of a heating test according to the Korean Industrial Standard KS F ISO 5660-1 [Combustion Performance Test - Heat Release, Smoke Generation, Mass Reduction Rate - Part 1: Heat Release Rate (Cone Calorimeter Method)], and it was confirmed that the flame retardant coating composition of the present invention can perform flame retardancy performance equivalent to the performance of semi-non-combustible materials, surpassing the performance of flame retardant materials.
실험예 2. 가스유해성 시험Experimental Example 2. Gas Toxicity Test
실험예 2의 가스유해성 시험에 관한 조건은 아래와 같다.The conditions for the gas toxicity test in Experimental Example 2 are as follows.
① 가스유해성 시험 조건① Gas toxicity test conditions
② 가스유해성 시험 시편 조건② Gas toxicity test specimen conditions
③ 시험 결과③ Test results
도 3 및 도 4를 참조하면, 상기 시편 4 시험 결과, 실험용 쥐의 평균행동정지 시간이 12분 이상인 것을 확인할 수 있었으며, 상기 시편 5의 시험 결과, 실험용 쥐의 평균행동정지 시간이 13분 이상인 것을 확인할 수 있었다.Referring to FIGS. 3 and 4, it was confirmed that the average behavioral suspension time of the experimental mice was 12 minutes or more in the test results of the above-mentioned specimen 4, and it was confirmed that the average behavioral suspension time of the experimental mice was 13 minutes or more in the test results of the above-mentioned specimen 5.
따라서, 본 발명은 한국산업표준 KS F 2271(건축물의 내장 재료 및 구조의 난연성 시험방법) 중 가스유해성 시험 결과, 건축자재등 품질인정 및 관리기준(국토교통부고시 제2023-24호)의 제24조 "준불연재료의 성능기준"을 충분히 만족하는 것을 확인할 수 있었으며, 본 발명의 난연성 코팅제 조성물은 난연재료의 성능을 뛰어넘어, 준불연재료의 성능에 준하는 난연성능을 수행할 수 있음을 확인할 수 있었다.Accordingly, it was confirmed that the present invention sufficiently satisfies the "Performance Criteria for Semi-Non-Combustible Materials" in Article 24 of the Quality Recognition and Management Standards for Building Materials, etc. (Ministry of Land, Infrastructure and Transport Notice No. 2023-24) as a result of the gas toxicity test in the Korean Industrial Standard KS F 2271 (Flame Retardancy Test Method for Building Interior Materials and Structures), and it was confirmed that the flame retardant coating composition of the present invention can perform flame retardancy performance equivalent to that of semi-non-combustible materials, surpassing the performance of flame retardant materials.
실험예 3. 추가 열적 시험Experimental Example 3. Additional thermal test
실험예 3의 추가 열적 시험에 관한 조건은 아래와 같다.The conditions for additional thermal testing in Experimental Example 3 are as follows.
① 추가 열적 시험 조건① Additional thermal test conditions
② 추가 열적 시험 시편 조건② Additional thermal test specimen conditions
③ 시험 결과③ Test results
도 5를 참조하면, 상기 시편 6의 실험 결과, 가열 개시 후 60분 경과한 시편에 있어, 전면 및 후면 모두 이상이 없음을 확인할 수 있었다.Referring to Fig. 5, the experimental results of the above specimen 6 showed that there were no abnormalities on either the front or back of the specimen 60 minutes after the start of heating.
따라서, 본 발명은 1200℃/60분의 추가 열적 시험에서도 문제 없으며, 열적 특성이 뛰어남을 확인할 수 있었다.Accordingly, it was confirmed that the present invention has excellent thermal characteristics and can withstand an additional thermal test of 1200℃/60 minutes without any problems.
실험예 4. 전기적 특성 시험Experimental Example 4. Electrical Characteristics Test
실험예 4의 전기적 특성 시험에 관한 조건은 아래와 같다.The conditions for the electrical characteristics test of Experimental Example 4 are as follows.
① 전기적 특성 시험 조건① Electrical characteristics test conditions
② 전기적 특성 시험 시편 조건② Electrical characteristics test specimen conditions
③ 시험 결과③ Test results
도 6을 참조하면, 상기 시편 7의 실험 결과, 상기 시편 7의 전기 저항이 3.48MΩ으로 측정되었으며, 절연 성능 시험 시 상기 시편 7의 전류가 0.16m로 측정되었으며, 내전압 시험 시 상기 시편 7의 외관에 아무 이상이 없음을 확인할 수 있었다.Referring to Fig. 6, as a result of the experiment on the specimen 7, the electrical resistance of the specimen 7 was measured as 3.48 MΩ, the current of the specimen 7 was measured as 0.16 m during the insulation performance test, and it was confirmed that there was no abnormality in the appearance of the specimen 7 during the withstand voltage test.
따라서, 본 발명은 전기적 특성이 매우 뛰어남을 확인할 수 있었다.Therefore, it was confirmed that the present invention has excellent electrical characteristics.
이상에서, 본 발명에 따른 실시예를 기준으로 본 발명의 구성과 특징을 설명하였으나 본 발명은 이에 한정되지 않으며, 본 발명의 사상과 범위 내에서 다양하게 변경 또는 변형할 수 있음은 본 발명이 속하는 기술분야의 당업자에게 명백한 것이며, 따라서 이와 같은 변경 또는 변형은 첨부된 특허청구범위에 속함을 밝혀둔다.In the above, the configuration and features of the present invention have been described based on embodiments according to the present invention, but the present invention is not limited thereto, and it is obvious to those skilled in the art that various changes or modifications can be made within the spirit and scope of the present invention, and therefore it is made clear that such changes or modifications fall within the scope of the appended patent claims.
Claims (12)
상기 실란은 알콕시 타입의 테트라에톡시실란(Tetraethoxysilane), 비닐트리메톡시실란(Vinyltrimethoxysilane) 및 3-아미노프로필트리메톡시실란(3-Aminopropyltrimethoxysilane)의 이들의 조합으로 이루어져 있는 것을 특징으로 하는 난연성 코팅제 조성물로서,
상기 난연성 코팅제 조성물 총 중량을 기준으로 유기수지 1 내지 10 중량%를 더 포함하고,
상기 암모늄 아미노 폴리 실라놀 인산염은 3-아미노프로필트리에톡시실란(3-Aminopropyl triethoxysilane)과 암모니아수가 첨가된 액상에 알카리형 실리카졸(sol)을 혼합 후, 산성 타입의 실리카졸(sol)과 혼합된 인산을 반응시켜 얻어낸 염(salt)을 인계 난연제에 습식 코팅 처리 및 건조하여 생성된 물질인 것이며,
상기 유기수지는 아크릴 수지를 필수성분으로 포함하는 것을 특징으로 하는 난연성 코팅제 조성물.
Characterized in that it comprises a ceramic powder treated with aluminosilicate, silane, ammonium amino polysilanol phosphate and ammonium amino polysilanol phosphate,
The above silane is a flame retardant coating composition characterized in that it is composed of a combination of alkoxy type tetraethoxysilane, vinyltrimethoxysilane and 3-aminopropyltrimethoxysilane.
The flame retardant coating composition further comprises 1 to 10 wt% of an organic resin based on the total weight of the composition,
The above ammonium amino polysilanol phosphate is a substance produced by mixing alkaline silica sol in a liquid phase to which 3-aminopropyl triethoxysilane and ammonia water have been added, reacting phosphoric acid mixed with acidic silica sol, and wet coating and drying the resulting salt on a phosphorus flame retardant.
A flame retardant coating composition characterized in that the organic resin contains acrylic resin as an essential component.
상기 난연성 코팅제 조성물은 조성물 총 중량을 기준으로 상기 알루미노 실리케이트 20 내지 50 중량%, 상기 실란 10 내지 30 중량%, 상기 암모늄 아미노 폴리 실라놀 인산염 20 내지 50 중량% 및 상기 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말 2 내지 5중량%를 포함하는 것을 특징으로 하는 난연성 코팅제 조성물.
In the first paragraph,
A flame retardant coating composition, characterized in that the flame retardant coating composition comprises 20 to 50 wt% of the aluminosilicate, 10 to 30 wt% of the silane, 20 to 50 wt% of the ammonium amino polysilanol phosphate, and 2 to 5 wt% of the ceramic powder treated with the ammonium amino polysilanol phosphate, based on the total weight of the composition.
상기 인계 난연제는 암모늄 폴리 포스페이트, 크레실 디페닐 포스페이트, 트리크레실 포스페이트, 트리크실릴 포스페이트, 트리페닐 포스페이트, 레졸시놀 비스(디페닐 포스페이트) 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나 이상인 것을 특징으로 하는 난연성 코팅제 조성물.
In the first paragraph,
A flame retardant coating composition, characterized in that the above-mentioned flame retardant is at least one selected from the group consisting of ammonium polyphosphate, cresyl diphenyl phosphate, tricresyl phosphate, tricylyl phosphate, triphenyl phosphate, resorcinol bis(diphenyl phosphate), and combinations thereof.
상기 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말은 담체 세라믹 분말 표면이 상기 암모늄 아미노 폴리 실라놀 인산염으로 습식 표면 처리되는 것을 특징으로 하는 난연성 코팅제 조성물.
In the first paragraph,
A flame retardant coating composition characterized in that the surface of the carrier ceramic powder treated with the above ammonium amino polysilanol phosphate is wet surface-treated with the above ammonium amino polysilanol phosphate.
상기 암모늄 아미노 폴리 실라놀 인산염과 상기 담체 세라믹 분말의 중량비는 4:6 인 것을 특징으로 하는 난연성 코팅제 조성물.
In Article 6,
A flame retardant coating composition, characterized in that the weight ratio of the ammonium amino polysilanol phosphate and the carrier ceramic powder is 4:6.
상기 담체 세라믹 분말은 마이카, 수산화마그네슘, 알루미늄, 알루미나, 아나타제 티탄 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나 이상인 것을 특징으로 하는 난연성 코팅제 조성물.
In Article 6.
A flame retardant coating composition, characterized in that the carrier ceramic powder is at least one selected from the group consisting of mica, magnesium hydroxide, aluminum, alumina, anatase titanium, and combinations thereof.
(b) 상기 알루미노 실리케이트에 실란을 투입하여 나노망상구조의 세라믹 올리고머가 제조되는 단계;
(c) 상기 세라믹 올리고머에 암모늄 아미노 폴리 실라놀 인산염을 투입하여 난연성 세라믹 올리고머 코팅제가 제조되는 단계;
(d) 상기 난연성 세라믹 올리고머 코팅제에 암모늄 아미노 폴리 실라놀 인산염이 처리된 세라믹 분말을 투입하여 난연성 코팅제 조성물이 제조되는 단계; 및
상기 난연성 코팅제 조성물에 유기수지가 투입되는 단계;를 더 포함하는 것을 특징으로 하는 난연성 코팅제 조성물의 제조 방법으로서,
상기 실란은 알콕시 타입의 테트라에톡시실란(Tetraethoxysilane), 비닐트리메톡시실란(Vinyltrimethoxysilane) 및 3-아미노프로필트리메톡시실란(3-Aminopropyltrimethoxysilane)의 이들의 조합으로 이루어져 있는 것을 특징으로 하고,
상기 난연성 코팅제 조성물 총 중량을 기준으로 유기수지 1 내지 10 중량%를 더 포함하고,
상기 암모늄 아미노 폴리 실라놀 인산염은 3-아미노프로필트리에톡시실란(3-Aminopropyl triethoxysilane)과 암모니아수가 첨가된 액상에 알카리형 실리카졸(sol)을 혼합 후, 산성 타입의 실리카졸(sol)과 혼합된 인산을 반응시켜 얻어낸 염(salt)을 인계 난연제에 습식 코팅 처리 및 건조하여 생성된 물질인 것이며,
상기 유기수지는 아크릴 수지를 필수성분으로 포함하는 것을 특징으로 하는 난연성 코팅제 조성물의 제조 방법.(a) a step of manufacturing aluminosilicate by synthesizing silicon oxide sol and aluminum nonahydrate;
(b) a step of manufacturing a ceramic oligomer having a nano-network structure by adding silane to the above aluminosilicate;
(c) a step of producing a flame retardant ceramic oligomer coating agent by adding ammonium amino polysilanol phosphate to the ceramic oligomer;
(d) a step of preparing a flame retardant coating composition by adding a ceramic powder treated with ammonium amino polysilanol phosphate to the flame retardant ceramic oligomer coating agent; and
A method for producing a flame retardant coating composition, characterized in that it further includes a step of adding an organic resin to the flame retardant coating composition;
The above silane is characterized by being composed of a combination of alkoxy type tetraethoxysilane, vinyltrimethoxysilane and 3-aminopropyltrimethoxysilane,
The flame retardant coating composition further comprises 1 to 10 wt% of an organic resin based on the total weight of the composition,
The above ammonium amino polysilanol phosphate is a substance produced by mixing alkaline silica sol in a liquid phase to which 3-aminopropyl triethoxysilane and ammonia water have been added, reacting phosphoric acid mixed with acidic silica sol, and wet coating and drying the resulting salt on a phosphorus flame retardant.
A method for producing a flame retardant coating composition, characterized in that the organic resin contains an acrylic resin as an essential component.
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