KR102566033B1 - FIRE RETARDANT COMPOSITION OF ECO-FRIENDLY FLOORING MATERIAL COMPRISING OF WATER SOLUBLE n-CYANIC ACID ESTER POLYMER RESIN AND HYBRID DIVIDED COMPLEX - Google Patents
FIRE RETARDANT COMPOSITION OF ECO-FRIENDLY FLOORING MATERIAL COMPRISING OF WATER SOLUBLE n-CYANIC ACID ESTER POLYMER RESIN AND HYBRID DIVIDED COMPLEX Download PDFInfo
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- acid ester
- cyanic acid
- semi
- silicate
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- 238000009408 flooring Methods 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229920003002 synthetic resin Polymers 0.000 title claims description 10
- 239000002952 polymeric resin Substances 0.000 title claims description 9
- 239000000463 material Substances 0.000 title description 20
- 239000003063 flame retardant Substances 0.000 title description 3
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 31
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000378 calcium silicate Substances 0.000 claims abstract description 25
- 235000012241 calcium silicate Nutrition 0.000 claims abstract description 25
- 229960003340 calcium silicate Drugs 0.000 claims abstract description 25
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 25
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 25
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006227 byproduct Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 229910052602 gypsum Inorganic materials 0.000 claims description 18
- 239000010440 gypsum Substances 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003546 flue gas Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000006477 desulfuration reaction Methods 0.000 claims description 13
- 230000023556 desulfurization Effects 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 239000004643 cyanate ester Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims description 6
- -1 polytetramethylene Polymers 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- WHULDTBQXVKIHX-UHFFFAOYSA-N propan-2-yl cyanate Chemical compound CC(C)OC#N WHULDTBQXVKIHX-UHFFFAOYSA-N 0.000 claims description 4
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical compound OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 claims description 3
- JXBPSENIJJPTCI-UHFFFAOYSA-N ethyl cyanate Chemical compound CCOC#N JXBPSENIJJPTCI-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- JYQQWQJCEUMXQZ-UHFFFAOYSA-N methyl cyanate Chemical compound COC#N JYQQWQJCEUMXQZ-UHFFFAOYSA-N 0.000 claims description 3
- CWHFDTWZHFRTAB-UHFFFAOYSA-N phenyl cyanate Chemical compound N#COC1=CC=CC=C1 CWHFDTWZHFRTAB-UHFFFAOYSA-N 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 17
- 230000000704 physical effect Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000004848 polyfunctional curative Substances 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004064 recycling Methods 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 7
- 239000004567 concrete Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 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 description 2
- MCYWEMHLHMUDBF-UHFFFAOYSA-N 2-methylpropyl cyanate Chemical compound CC(C)COC#N MCYWEMHLHMUDBF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 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
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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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
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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
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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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
본 발명은 수경화성 n-시안산 에스테르계 중합수지 및 하이브리드 분체로 이루어지는 준불연 친환경 바닥재 조성물에 관한 것으로서, 더욱 상세하게는, 유해물질을 함유하지 않으면서 준불연 특성을 나타내어 다양한 바닥재 시공에 적합한 준불연 친환경 바닥재 조성물에 관한 것이다.The present invention relates to a semi-incombustible eco-friendly flooring composition composed of a hydraulically curable n-cyanate ester-based polymeric resin and a hybrid powder, and more particularly, to a semi-incombustible flooring composition suitable for various flooring constructions because it does not contain harmful substances and exhibits quasi-incombustible properties. It relates to a non-combustible eco-friendly flooring composition.
아파트 지하 주차장, 운동 시설, 건물의 옥상 등에 적용되는 바닥 마감재는 단순한 방진이나 마감 개념에서 더 나아가 내구성 확보와 품질의 고급화와 같은 요구 사항이 반영된 제품이 개발되고 있다. 콘크리트 바닥면에 시공하는 일반적인 바닥재로는 에폭시수지, 우레탄수지, 비닐수지 등 합성수지 도료형 바닥 마감재와 시멘트계 바닥 마감재가 사용되고 있다.Floor finishing materials applied to apartment underground parking lots, sports facilities, and building rooftops are developing products that reflect requirements such as securing durability and high quality, going beyond simple dustproofing or finishing concepts. As general flooring materials constructed on concrete floors, synthetic resin paint-type floor finishing materials such as epoxy resin, urethane resin, and vinyl resin and cement-based floor finishing materials are used.
널리 사용되고 있는 에폭시 및 우레탄 수지는 굴곡성, 신축성, 방진성, 내오염성, 작업성, 속건성, 내수성이 우수할 뿐 아니라 초기 접착력이 매우 탁월하며, 다량의 각종 충진제의 사용이 가능한 이점이 있다. 에폭시 수지나 우레탄 수지를 포함하는 마감재로 양생이 끝난 콘크리트 바닥 표면에 일정 두께 이상의 도막을 형성하고 경화시키면, 시공 초기에는 외부 환경으로부터 콘크리트 바닥을 효율적으로 차단하여 단기간에 우수한 마감효과를 발휘할 수 있다.Epoxy and urethane resins, which are widely used, have excellent flexibility, elasticity, dustproofness, stain resistance, workability, quick-drying, and water resistance, as well as excellent initial adhesive strength, and have the advantage of being able to use a large amount of various fillers. When a coating film of a certain thickness or more is formed and cured on the surface of a cured concrete floor with a finishing material containing epoxy resin or urethane resin, it is possible to effectively block the concrete floor from the external environment at the beginning of construction and achieve an excellent finishing effect in a short period of time.
그러나 에폭시나 우레탄 수지를 사용하는 바닥재는 휘발성 유기화합물이 포함된 제품이 대부분이므로 작업자의 건강을 위협하며 시공 후 잔여 용제의 휘발로 인한 악영향을 미칠 수 있고 화재에도 취약할 수 있다.However, since most of the flooring materials using epoxy or urethane resin contain volatile organic compounds, they threaten the health of workers, may have adverse effects due to volatilization of residual solvents after construction, and may be vulnerable to fire.
출원인은 이러한 문제점을 해결하기 위하여 대한민국 등록특허공보 10-1067471호를 통해 시안산 에스테르계 단량체(monomer)를 산 촉매하에서 반응시킨 중합수지 100 중량부 및 글리콜산과 다가 알코올 1~30 중량% 및 물 70~99 중량%로 구성된 수용액 상태의 수경화제 20~1,200 중량부를 포함하는 바닥재 조성물을 통해 친환경적이고 무취 특성을 나타내는 바닥재를 개발한 바 있다. 상기 바닥재 조성물은 오염 물질 방출 성능을 측정한 결과 KS F 4937에 따른 성능 기준을 만족하는 것으로 나타났다.In order to solve this problem, the applicant, through Korean Patent Registration No. 10-1067471, 100 parts by weight of a polymeric resin reacted with a cyanic acid ester monomer under an acid catalyst, 1 to 30% by weight of glycolic acid and a polyhydric alcohol, and 70% water A flooring material exhibiting eco-friendly and odorless characteristics has been developed through a flooring composition containing 20 to 1,200 parts by weight of a water curing agent in an aqueous solution consisting of ~99% by weight. The flooring composition was found to satisfy the performance criteria according to KS F 4937 as a result of measuring pollutant emission performance.
최근에는 바닥재 뿐만 아니라 각종 건축용 소재의 원료로 산업 부산물을 재활용하는 기술이 개발되고 있다.Recently, technologies for recycling industrial by-products as raw materials for various building materials as well as flooring materials have been developed.
출원인은 대한민국 등록특허공보 10-2248986호를 통해 콘크리트 혼화제를 구성하는 실리카 하이브리드 규불화염 복합화합물을 제조하기 위한 원료로 테트라오르소실리케이트(TEOS)의 정제공정에서 발생하는 부산물인 저순도 TEOS를 재활용하여 규산염 성분으로 재활용하는 기술을 개발한 바 있으며, 대한민국 등록특허공보 10-2396556호를 통해 바닥 마감재 조성물을 구성하는 분체를 제조할 때 산화칼슘(CaO)을 60 내지 70 질량% 함유하는 배연탈황석고를 원료로 하는 기술을 개발한 바 있다.The applicant, through Korean Patent Publication No. 10-2248986, has recycled low-purity TEOS, a by-product generated in the refining process of tetraorthosilicate (TEOS), as a raw material for producing a silica hybrid silicofluoride composite compound constituting a concrete admixture. A technology for recycling as a silicate component has been developed, and through Korean Patent Registration No. 10-2396556, flue gas desulfurization gypsum containing 60 to 70% by mass of calcium oxide (CaO) is used when preparing the powder constituting the floor finishing composition. Developed raw material technology.
따라서 이러한 폐자원을 재활용하면서도 오염 물질 방출량이 적고 종래의 바닥재 조성물에 상응하는 물성을 나타내는 바닥재를 개발한다면 경제성 및 자원 재활용의 측면에서 장점을 나타낼 수 있다.Therefore, if a flooring material that exhibits physical properties corresponding to those of conventional flooring compositions with low emission of pollutants while recycling such waste resources is developed, advantages can be shown in terms of economic feasibility and recycling of resources.
본 발명은 상기와 같은 종래기술을 감안하여 안출된 것으로서, 산업 부산물을 재활용하여 이를 원료로 함으로써 제조되는 준불연 친환경 바닥재 조성물을 제공하는 것을 그 목적으로 한다.The present invention has been made in view of the prior art as described above, and an object of the present invention is to provide a semi-nonflammable eco-friendly flooring composition prepared by recycling industrial by-products and using them as raw materials.
또한, 바닥재 조성물에 요구되는 물성을 충족하여 내충격성, 부착강도, 윤하중 저항성능, 수밀성능 등의 물성이 우수한 바닥 시공을 할 수 있으면서도 TVOC와 같은 유해 물질이 발생하지 않는 바닥재 조성물을 제공하는 것을 그 목적으로 한다.In addition, it is to provide a flooring composition that does not generate harmful substances such as TVOC while meeting the physical properties required for the flooring composition to perform floor construction with excellent physical properties such as impact resistance, adhesive strength, wheel load resistance performance, and watertightness performance. The purpose.
또한, 유무기 하이브리드형 바닥재 조성물을 구성함으로써 준불연 성능을 나타낼 수 있는 친환경 바닥재 조성물을 제공하는 것을 그 목적으로 한다.In addition, an object of the present invention is to provide an eco-friendly flooring composition capable of exhibiting semi-incombustible performance by configuring an organic-inorganic hybrid flooring composition.
상기 목적을 달성하기 위한 본 발명의 준불연 친환경 바닥재 조성물은 n-시안산 에스테르계 수지, 수경화제 및 칼슘-규산염 분체로 이루어지는 준불연 친환경 바닥재 조성물로서, 상기 n-시안산 에스테르계 수지는 규산염 함유 n-시안산 에스테르계 수지이며, 상기 칼슘-규산염 분체는 배연탈황석고 및 황토를 포함하는 것을 특징으로 한다.The semi-nonflammable eco-friendly flooring composition of the present invention for achieving the above object is a semi-nonflammable eco-friendly flooring composition composed of n-cyanate ester-based resin, a water curing agent and calcium-silicate powder, wherein the n-cyanic acid ester-based resin contains silicate It is an n-cyanic acid ester-based resin, and the calcium-silicate powder is characterized in that it includes flue gas desulfurized gypsum and ocher.
이때, 상기 규산염 함유 n-시안산 에스테르계 수지는 시안산 메틸(CH3OC≡N), 시안산 에틸(C2H5OC≡N), 시안산 이소프로필(i-C3H7OC≡N), 시안산 이소부틸(i-C4H9OC≡N) 및 시안산 페닐(C6H5OC≡N))에서 선택되는 어느 하나의 n-시안산 에스테르계 단량체를 산 촉매 하에서 중합 반응하여 중합수지를 제조하고, 상기 중합수지 100 중량부에 대하여 고형분(SiO2)의 함량이 부산물의 5 중량% 미만인 저순도 테트라오르소실리케이트에 산 촉매를 가하여 가수분해하여 수득된 규산염 수용액 100 내지 200 중량부를 혼합하여 제조되는 것일 수 있다.At this time, the silicate-containing n-cyanate ester-based resin is methyl cyanate (CH 3 OC≡N), ethyl cyanate (C 2 H 5 OC≡N), isopropyl cyanate (iC 3 H 7 OC≡N) , isobutyl cyanate (iC 4 H 9 OC≡N) and phenyl cyanate (C 6 H 5 OC≡N)) by polymerization of any one n-cyanic acid ester-based monomer selected from , and mixing 100 to 200 parts by weight of an aqueous silicate solution obtained by hydrolysis by adding an acid catalyst to low-purity tetraorthosilicate having a solid content (SiO 2 ) of less than 5% by weight of by-products based on 100 parts by weight of the polymerization resin. It may be manufactured by
또한, 상기 수경화제는 글리콜산(glycolic acid) 및 다가 알코올을 함유하는 수용액으로서, 상기 다가 알코올은 1,4-부틴디올, 에틸렌글리콜, 프로필렌글리콜, 디에틸렌글리콜 및 폴리테트라메틸렌글리콜 중에서 선택되는 어느 하나일 수 있다.In addition, the water curing agent is an aqueous solution containing glycolic acid and a polyhydric alcohol, and the polyhydric alcohol is any one selected from 1,4-butyndiol, ethylene glycol, propylene glycol, diethylene glycol and polytetramethylene glycol. can be one
또한, 상기 배연탈황석고는 산화칼슘(CaO)을 30 내지 50 질량% 함유하는 것일 수 있다.In addition, the flue gas desulfurization gypsum may contain 30 to 50% by mass of calcium oxide (CaO).
또한, 상기 준불연 친환경 바닥재 조성물은 n-시안산 에스테르계 수지 100 중량부에 대하여, 수경화제 50 내지 100 중량부 및 칼슘-규산염 분체 100 내지 150 중량부로 이루어지는 것일 수 있다.In addition, the semi-incombustible eco-friendly flooring composition may be composed of 50 to 100 parts by weight of a water curing agent and 100 to 150 parts by weight of a calcium-silicate powder based on 100 parts by weight of an n-cyanic acid ester-based resin.
본 발명의 바닥재 조성물은 산업 부산물을 재활용하여 이를 원료로 하여 친환경 소재이면서도 바닥 시공에 적합한 물성을 나타낼 수 있다.The flooring composition of the present invention can exhibit physical properties suitable for floor construction while being an eco-friendly material by recycling industrial by-products and using them as raw materials.
또한, TVOC와 같은 유해 물질 발생이 없으면서도 바닥 시공에 요구되는 내충격성, 부착강도, 윤하중 저항성능, 수밀성능 등의 물성을 충족시키는 효과를 나타낼 수 있다.In addition, it can show the effect of satisfying physical properties such as impact resistance, adhesive strength, wheel load resistance performance, and watertight performance required for floor construction without generating harmful substances such as TVOC.
또한, 유무기 하이브리드형으로 바닥재 조성물을 구성함으로써 종래의 시안산 에스테르계 수지를 포함하는 바닥재 조성물에 비해 준불연 성능이 향상된 바닥재 조성물을 제공할 수 있다.In addition, by configuring the flooring composition in an organic-inorganic hybrid type, it is possible to provide a flooring composition with improved semi-incombustible performance compared to a flooring composition containing a conventional cyanate ester-based resin.
도 1은 실시예 1의 바닥재 조성물로 제작한 시험체에 화염을 분사한 후의 상태(a) 및 비교예 2의 에폭시계 바닥재 조성물로 제작한 시험체에 화염을 분사한 후의 상태(b)를 관찰한 사진이다.
도 2는 실시예 1의 바닥재 조성물로 제조된 시험체의 준불연 시험 성적표이다.1 is a photograph of a state after spraying a flame on a test body made of a flooring composition of Example 1 (a) and a state after spraying a flame on a test body made of an epoxy-based flooring composition of Comparative Example 2 (b) am.
Figure 2 is a semi-incombustible test report card of the test body made of the flooring composition of Example 1.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 준불연 친환경 바닥재 조성물은 n-시안산 에스테르계 수지, 수경화제 및 칼슘-규산염 분체로 이루어지는 준불연 친환경 바닥재 조성물로서, 상기 n-시안산 에스테르계 수지는 규산염 함유 n-시안산 에스테르계 수지이며, 상기 칼슘-규산염 분체는 배연탈황석고 및 황토를 포함하는 것을 특징으로 한다.The semi-nonflammable eco-friendly flooring composition of the present invention is a semi-nonflammable eco-friendly flooring composition composed of n-cyanic acid ester-based resin, a water curing agent and calcium-silicate powder, wherein the n-cyanic acid ester-based resin is a silicate-containing n-cyanic acid ester-based It is a resin, and the calcium-silicate powder is characterized in that it includes flue gas desulfurized gypsum and ocher.
상기 n-시안산 에스테르계 수지는 출원인이 대한민국 등록특허공보 10-1067471호를 통해 바닥재 조성물을 구성하는 중합수지로서 사용한 것으로서 바닥재 조성물의 특성을 충족시키면서도 유해물질을 함유하지 않는 친환경 바닥재 조성물을 제공하고 있다.The n-cyanic acid ester-based resin is used as a polymeric resin constituting the flooring composition by the applicant through Korean Patent Registration No. 10-1067471, and provides an eco-friendly flooring composition that does not contain harmful substances while satisfying the characteristics of the flooring composition there is.
따라서 본 발명에서는 수지로서 상기 종래기술에 사용되는 n-시안산 에스테르계 수지를 사용하되 하이브리드 분체 대신 산업 부산물을 재활용한 무기 성분을 채용함으로써 유무기 하이브리드형 바닥재 조성물을 구성하는 것을 기술적 특징으로 한다.Therefore, in the present invention, the technical feature is to configure an organic-inorganic hybrid type flooring composition by using an n-cyanic acid ester-based resin used in the prior art as a resin, but employing an inorganic component recycled from industrial by-products instead of hybrid powder.
이를 위하여 사용되는 상기 n-시안산 에스테르계 수지는 규산염 성분이 함유되는 규산염 함유 n-시안산 에스테르계 수지를 사용하는 것이 바람직하다. 구체적으로, 상기 규산염 함유 n-시안산 에스테르계 수지는 시안산 메틸(CH3OC≡N), 시안산 에틸(C2H5OC≡N), 시안산 이소프로필(i-C3H7OC≡N), 시안산 이소부틸(i-C4H9OC≡N) 및 시안산 페닐(C6H5OC≡N))에서 선택되는 어느 하나의 n-시안산 에스테르계 단량체를 산 촉매 하에서 60±5℃의 온도에서 1.5 내지 2시간 동안 중합 반응하여 중합수지를 제조하고, 상기 중합수지에 대해 고형분(SiO2)의 함량이 부산물의 5 중량% 미만인 저순도 테트라오르소실리케이트(TEOS)에 산 촉매를 가하여 가수분해함으로써 수득된 규산염 수용액을 혼합하되 상기 중합수지 100 중량부에 대하여 규산염 수용액 100 내지 200 중량부를 혼합함으로써 제조될 수 있다. 이와 같이 제조된 n-시안산 에스테르계 수지는 고분자 쇄 내에 규산염이 분산되어 있으며, 이후 칼슘-규산염 분체와 혼합될 때 상용성을 증가시켜 준불연 성능을 향상시킬 수 있게 된다.As the n-cyanic acid ester-based resin used for this purpose, it is preferable to use a silicate-containing n-cyanic acid ester-based resin containing a silicate component. Specifically, the silicate-containing n-cyanate ester-based resin is methyl cyanate (CH 3 OC≡N), ethyl cyanate (C 2 H 5 OC≡N), isopropyl cyanate (iC 3 H 7 OC≡N ), isobutyl cyanate (iC 4 H 9 OC≡N) and phenyl cyanate (C 6 H 5 OC≡N)) at 60±5° C. under an acid catalyst. A polymerization resin is prepared by polymerization at a temperature of 1.5 to 2 hours, and an acid catalyst is added to low-purity tetraorthosilicate (TEOS) having a solid content (SiO 2 ) of less than 5% by weight of by-products for the polymerization resin. It may be prepared by mixing an aqueous silicate solution obtained by hydrolysis and mixing 100 to 200 parts by weight of an aqueous silicate solution with respect to 100 parts by weight of the polymerization resin. In the n-cyanic acid ester-based resin prepared as described above, silicate is dispersed in the polymer chain, and then, when mixed with calcium-silicate powder, compatibility is increased to improve semi-incombustible performance.
또한, 상기 수경화제는 상기 n-시안산 에스테르계 수지와 함께 상기 유무기 하이브리드형 바닥재 조성물의 유기 성분을 구성하는 것으로서, 글리콜산(glycolic acid) 및 다가 알코올을 함유하는 수용액이며, 상기 다가 알코올로는 1,4-부틴디올, 에틸렌글리콜, 프로필렌글리콜, 디에틸렌글리콜 및 폴리테트라메틸렌글리콜 중에서 선택되는 어느 하나를 사용할 수 있다.In addition, the water curing agent constitutes an organic component of the organic-inorganic hybrid type flooring composition together with the n-cyanic acid ester-based resin, and is an aqueous solution containing glycolic acid and a polyhydric alcohol, with the polyhydric alcohol may use any one selected from 1,4-butyndiol, ethylene glycol, propylene glycol, diethylene glycol and polytetramethylene glycol.
구체적으로 상기 수경화제는 글리콜산 및 다가 알코올을 1:1의 증량비로 혼합하며, 상기 글리콜산 및 다가 알코올에 대한 물의 비율이 1:10 내지 1:15의 중량비가 되도록 수중 분산시켜 수용액 형태로 제조할 수 있다.Specifically, the water curing agent is prepared in the form of an aqueous solution by mixing glycolic acid and polyhydric alcohol in an increasing ratio of 1: 1, and dispersing in water so that the ratio of water to glycolic acid and polyhydric alcohol is in a weight ratio of 1: 10 to 1: 15 can do.
상기 유기 성분을 구성하는 상기 n-시안산 에스테르계 수지와 수경화제는 1:0.2 내지 1:0.5의 비율로 혼합될 수 있는데, 이를 통해 수지와 글리콜산, 알코올 성분이 혼합된 수용액이 형성되게 된다.The n-cyanic acid ester-based resin and the hydraulic curing agent constituting the organic component may be mixed in a ratio of 1: 0.2 to 1: 0.5, through which an aqueous solution in which the resin, glycolic acid, and alcohol components are mixed is formed. .
또한, 종래기술에서는 n-시안산 에스테르계 수지, 수경화제 및 무기 성분인 하이브리드 분체를 1:0.5:1로 혼합하여 수지와 동일한 양의 하이브리드 분체를 혼합하고 있다. 또한, 상기 하이브리드 분체로는 칼슘아세테이트 35중량%, 탄산칼슘 7중량%, 수산화칼슘 3중량%, α형 반수석고 10중량%로 구성된 칼슘염계 화합물 55중량%와 오르토규산염 20중량%, 가공규산염 15중량% 및 황토 10중량%로 구성된 규산염계 화합물 45중량%로 이루어진 칼슘-규산염계 하이브리드 분체를 사용하고 있다.In addition, in the prior art, n-cyanic acid ester-based resin, a hydraulic curing agent, and hybrid powder as an inorganic component are mixed in a ratio of 1:0.5:1, and the hybrid powder is mixed in the same amount as the resin. In addition, the hybrid powder includes 55% by weight of a calcium salt compound composed of 35% by weight of calcium acetate, 7% by weight of calcium carbonate, 3% by weight of calcium hydroxide, and 10% by weight of α-type hemihydrate gypsum, 20% by weight of orthosilicate, and 15% by weight of engineered silicate. Calcium-silicate-based hybrid powder consisting of 45% by weight of a silicate-based compound composed of % and 10% by weight of loess is used.
본 발명에서는 종래기술의 칼슘-규산염계 하이브리드 분체 대신 산업 부산물을 재활용하여 제조된 칼슘-규산염 분체를 무기 성분으로 사용하면서도 종래기술의 바닥재와 비슷한 정도의 물성을 나타내도록 하고 있다. 이러한 칼슘-규산염 분체는 규산염 함유 n-시안산 에스테르계 수지 및 수경화제와의 상용성이 우수한 것으로 나타났다.In the present invention, instead of the calcium-silicate hybrid powder of the prior art, calcium-silicate powder manufactured by recycling industrial by-products is used as an inorganic component, while exhibiting physical properties similar to those of the prior art flooring material. This calcium-silicate powder was found to have excellent compatibility with the silicate-containing n-cyanic acid ester-based resin and the hydraulic curing agent.
상기 칼슘-규산염 분체는 배연탈황석고 및 황토를 포함하는 것으로서, 구체적으로, 배연탈황석고 50 내지 60 중량부, 황토 30 내지 40 중량부로 이루어지는 것을 사용할 수 있다.The calcium-silicate powder includes flue gas desulfurization gypsum and loess, and specifically, it may be used that consists of 50 to 60 parts by weight of flue gas desulfurization gypsum and 30 to 40 parts by weight of loess.
상기 배연탈황석고는 유동층 보일러 탈황공정에서 발생하는 산업 부산물로서, 산화칼슘(CaO), 삼산화황(SO3), 산화규소(SiO2), 산화마그네슘(MgO) 등을 주성분으로 하고 있다. 상기 탈황석고는 발생요인에 따라 다양한 성분비로 이루어진다. 출원인은 대한민국 등록특허공보 10-2396556호를 통해 바닥 마감재 조성물을 구성하는 분체를 제조할 때 산화칼슘(CaO)을 60 내지 70 질량% 함유하는 배연탈황석고를 사용할 때 가장 좋은 효과를 얻는 것을 확인하였다.The flue gas desulfurization gypsum is an industrial by-product generated in a fluidized bed boiler desulfurization process, and has calcium oxide (CaO), sulfur trioxide (SO 3 ), silicon oxide (SiO 2 ), magnesium oxide (MgO), and the like as main components. The desulfurized gypsum is composed of various component ratios according to occurrence factors. The applicant confirmed through Korean Patent Registration No. 10-2396556 that the best effect was obtained when using flue gas desulfurization gypsum containing 60 to 70% by mass of calcium oxide (CaO) when preparing powder constituting the floor finishing composition. .
그러나 본 발명에서와 같이 칼슘-규산염 분체는 규산염 함유 n-시안산 에스테르계 수지와 배합되며, 최종적으로 수득되는 바닥재의 성분과 함량 차이를 고려할 때 산화칼슘을 30 내지 50 질량% 함유하는 배연탈황석고를 사용하는 것이 바람직한 것으로 나타났다. 산화칼슘의 함량이 너무 낮거나 너무 높은 배연탈황석고를 사용할 경우 규산염 성분과의 함량 차이가 커져서 칼슘-규산염 성분으로서의 효과를 충분히 얻지 못하는 것으로 나타났다.However, as in the present invention, the calcium-silicate powder is blended with a silicate-containing n-cyanic acid ester-based resin, and considering the component and content difference of the finally obtained floor ash, the flue gas desulfurized gypsum containing 30 to 50% by mass of calcium oxide It has been shown that it is preferable to use It was found that when the flue gas desulfurization gypsum with too low or too high calcium oxide content was used, the effect as a calcium-silicate component was not sufficiently obtained because the content difference with the silicate component increased.
상기 산화칼슘은 이산화탄소와 반응하여 탄산칼슘을 형성하며 이를 통해 표면 평탄성에 영향을 미치는 것으로 나타났는데, 본 발명에서는 산화칼슘의 함량이 상대적으로 작은 배연탈황석고를 사용하더라도 바닥 시공 후의 표면 특성이 양호한 것으로 나타났다. 이는 수용액 상에서 용해된 산화칼슘이 저순도 TEOS와 반응하며 산화칼슘의 함량이 너무 많은 경우 미반응 칼슘 이온의 농도가 높아져 바닥 시공 후의 표면 특성에 영향을 미치기 때문으로 생각된다.It was found that the calcium oxide reacts with carbon dioxide to form calcium carbonate, thereby affecting the surface flatness. In the present invention, even if a flue gas desulfurized gypsum having a relatively small content of calcium oxide is used, the surface properties after floor construction are good. appear. This is considered to be because calcium oxide dissolved in the aqueous solution reacts with low-purity TEOS, and when the content of calcium oxide is too large, the concentration of unreacted calcium ions increases, affecting the surface properties after floor construction.
상기 배연탈황석고는 50 내지 60 중량부의 범위에서 사용되는데, 사용량이 너무 많을 경우 바닥 시공시 물성이 저하되는 문제점이 있으며, 너무 적게 사용할 경우 산업 부산물의 재활용이라는 이점을 얻을 수 없으므로 상기 범위에서 사용하는 것이 바람직하다.The flue gas desulfurization gypsum is used in the range of 50 to 60 parts by weight. If the amount is too large, there is a problem in that physical properties are deteriorated during floor construction, and when used too little, the advantage of recycling industrial by-products cannot be obtained. it is desirable
또한, 상기 황토는 천연 클레이 성분으로서 유해물질을 함유하지 않으며, 무기 성분에 사용됨으로써 적절한 점성과 바닥 시공시 강도를 제공하는 기능을 나타낸다. 종래기술에서도 칼슘-규산염계 하이브리드 분체의 규산염계 화합물로 사용할 수 있는 일 성분으로 황토가 제시되고 있는데, 본 발명에서는 배연탈황석고를 칼슘염 성분으로 사용하기 때문에 이와 상용성이 가장 좋은 재료로서 황토를 선택하여 사용하고 있다.In addition, the loess does not contain harmful substances as a natural clay component, and exhibits a function of providing appropriate viscosity and strength during floor construction by being used as an inorganic component. In the prior art, ocher is proposed as one component that can be used as a silicate compound of calcium-silicate hybrid powder. In the present invention, since flue gas desulfurization gypsum is used as a calcium salt component, ocher is the most compatible material. selected and used.
상기 황토는 30 내지 40 중량부의 범위에서 사용되는데, 함량이 너무 적으면 바닥 시공을 위한 충분한 유동성을 얻지 못해 작업성이 저하될 수 있으며, 너무 많으면 바닥재 조성물 내에서 층 분리 현상이 발생하여 바닥재 자체의 강도가 저하될 수 있다.The loess is used in the range of 30 to 40 parts by weight. If the content is too small, sufficient fluidity for floor construction may not be obtained, and workability may be deteriorated. strength may be reduced.
또한, 상기 저순도 TEOS는 TEOS의 정제공정에서 발생하는 산업 부산물로서 고형분(SiO2)의 함량이 부산물의 5 중량% 미만, 바람직하게는 2 내지 5 중량%인 수용액이다. 출원인은 대한민국 등록특허공보 10-2248986호를 통해 콘크리트 혼화제를 구성하는 실리카 하이브리드 규불화염 복합 화합물을 제조할 때 상기 저순도 TEOS와 규불화염을 혼합하여 제조함으로써 겔화된 상태의 복합체를 얻고 있다.In addition, the low-purity TEOS is an industrial by-product generated in a TEOS purification process, and is an aqueous solution having a solid content (SiO 2 ) of less than 5% by weight, preferably 2 to 5% by weight. The applicant obtained a composite in a gelled state by mixing the low-purity TEOS and the fluorosilicosodium salt when preparing a silica hybrid fluorosilicosodium compound constituting a concrete admixture through Korean Patent Registration No. 10-2248986.
본 발명에서는 상기 저순도 TEOS를 이용하여 규산염 함유 n-시안산 에스테르계 수지를 제조하고 있는데, 상기 저순도 TEOS는 수용액 상태이므로 가수분해를 하면 실리카 수화물(Si(OH)x) 형태의 규산염을 형성하게 된다. 상기 수지의 고분자 쇄 내에 분산되는 규산염은 칼슘염 성분 및 황토와의 반응성이 높아 칼슘-규산염을 안정적으로 형성하고 수지와 무기 성분의 상용성을 향상시킴으로써 결과적으로 난연성을 높일 수 있게 된다.In the present invention, a silicate-containing n-cyanic acid ester-based resin is prepared using the low-purity TEOS. Since the low-purity TEOS is in an aqueous solution, hydrolysis forms a silicate in the form of silica hydrate (Si(OH) x ) will do The silicate dispersed in the polymer chain of the resin has high reactivity with the calcium salt component and loess, so that calcium-silicate is stably formed and compatibility between the resin and the inorganic component is improved, resulting in increased flame retardancy.
상기 저순도 TEOS를 n-시안산 에스테르계 수지와 배합시키지 않고 무기 성분으로서 혼합하는 경우에는 고형분 함량이 낮아 다량의 수분을 함유하는 재료의 특성 상 수지와의 상용성 뿐만 아니라 물성을 저하시키는 요인이 될 수 있으므로 규산염 함유 n-시안산 에스테르계 수지의 형태로 제조하여 사용할 때와 달리 충분한 난연성을 확보할 수 없게 되며 유동성이 저하로 인해 바닥 시공에서 작업성이 저하되는 것으로 나타났다.When the low-purity TEOS is mixed as an inorganic component without blending with the n-cyanic acid ester-based resin, it is a factor that deteriorates physical properties as well as compatibility with the resin due to the nature of the material containing a large amount of moisture due to its low solid content. Therefore, unlike when prepared and used in the form of a silicate-containing n-cyanic acid ester-based resin, it is not possible to secure sufficient flame retardancy, and due to a decrease in fluidity, workability in floor construction is reduced.
본 발명의 바닥재 조성물은 유무기 하이브리드형 친환경 바닥재 조성물로서 상기와 같은 유기 성분 및 무기 성분이 조합되어 구성되는데, 구체적으로는 n-시안산 에스테르계 수지 100 중량부에 대하여, 수경화제 50 내지 100 중량부 및 칼슘-규산염 분체 100 내지 150 중량부로 이루어지는 것이 바람직하다. 특히, 수경화제 및 칼슘-규산염 분체는 n-시안산 에스테르계 수지와 배합할 때의 비율을 적절한 범위에서 조절해야 바닥 시공에 적합한 특성을 얻을 수 있으며, 상기 범위를 벗어난 조합에서는 바닥 시공시 작업성이 저하되거나 시공 후 바닥의 내구성이 저하되는 것으로 나타났다. 또한, 칼슘-규산염 분체를 포함함으로써 난연 성능이 우수하여 준불연 특성을 충족시키는 것으로 나타났다.The flooring composition of the present invention is an organic-inorganic hybrid eco-friendly flooring composition composed of a combination of organic and inorganic components as described above. It is preferably composed of 100 to 150 parts by weight of calcium-silicate powder. In particular, when mixing the water curing agent and calcium-silicate powder with the n-cyanic acid ester-based resin, the ratio must be adjusted within an appropriate range to obtain properties suitable for floor construction, and in combinations outside the above range, workability during floor construction It was found that the durability of the floor deteriorated after construction. In addition, by including the calcium-silicate powder, the flame retardant performance was excellent and it was found to satisfy the semi-incombustible characteristics.
본 발명에 따른 친환경 바닥재 조성물이 바닥 시공에 적합한지 여부를 확인하기 위하여 다음과 같이 시험평가를 실시하였다.In order to confirm whether the eco-friendly flooring composition according to the present invention is suitable for floor construction, a test evaluation was conducted as follows.
[실시예][Example]
바닥재 조성물은 표 1과 같은 성분과 함량으로 제조되었으며, n-시안산 에스테르계 수지, 수경화제 및 칼슘-규산염 분체를 각각 제조한 후 이를 혼합하는 공정을 통해 조성물을 제조하였다.The flooring composition was prepared with the ingredients and contents shown in Table 1, and the composition was prepared through a process of preparing n-cyanic acid ester-based resin, a water curing agent, and calcium-silicate powder, respectively, and then mixing them.
n-시안산 에스테르계 수지는 규산염 함유 n-시안산 에스테르계 수지로서, 시안산 이소프로필 단량체를 60±5℃의 반응 온도 및 질소 분위기에서 1N의 염산 촉매를 부가하여 pH 5 내지 6이 되도록 한 후 2시간 동안 반응시켜 중합수지를 제조하고, 저순도 TEOS에 1N의 염산 촉매를 부가하여 가수분해함으로써 수득된 규산염 수용액을 제조한 후, 상기 중합수지 100 중량부에 상기 규산염 수용액 150 중량부를 혼합하고 여과 및 진공건조하여 수득된 수지를 사용하였다.The n-cyanic acid ester-based resin is a silicate-containing n-cyanic acid ester-based resin, which is prepared by adding 1N hydrochloric acid catalyst to an isopropyl cyanate monomer at a reaction temperature of 60 ± 5 ° C. and a nitrogen atmosphere to have a pH of 5 to 6. After reacting for 2 hours to prepare a polymeric resin, adding a 1N hydrochloric acid catalyst to low-purity TEOS to prepare an aqueous silicate solution obtained by hydrolysis, and then mixing 150 parts by weight of the aqueous silicate solution with 100 parts by weight of the polymeric resin, A resin obtained by filtration and vacuum drying was used.
또한, 수경화제는 글리콜산 및 1,4-부탄디올을 1:1의 중량비로 혼합하여 혼합물을 제조하고, 상기 혼합물과 물을 1:10의 중량비로 혼합하여 수용액 형태로 제조하였다.In addition, the hydraulic curing agent was prepared in the form of an aqueous solution by mixing glycolic acid and 1,4-butanediol in a weight ratio of 1:1 to prepare a mixture, and mixing the mixture and water in a weight ratio of 1:10.
또한, 칼슘-규산염 분체는 배연탈황석고 65 중량부 및 황토 35 중량부를 혼합하여 슬러리화한 후 이를 스프레이 드라이어로 건조하여 제조하였다. 배탈황석고는 CaO 함량이 32.07 질량%인 것을 사용하였으며, 저순도 TEOS는 고형분 함량이 3 중량%인 수용액을 사용하였다.In addition, the calcium-silicate powder was prepared by mixing 65 parts by weight of flue gas desulfurized gypsum and 35 parts by weight of loess to form a slurry, and then drying it with a spray dryer. The stomach desulfurization gypsum used a CaO content of 32.07% by mass, and low-purity TEOS used an aqueous solution having a solid content of 3% by weight.
규산염 함유 n-시안산 에스테르계 수지, 수경화제 및 칼슘-규산염 분체를 1:0.5:1의 중량비로 혼합한 조성물(실시예 1), 1:0.5:1.5의 중량비로 혼합한 조성물(실시예 2)를 각각 제조한 후, 바탕판에 도포하여 바닥재의 평균 두께가 3.5㎜인 시험체를 제조하였다.A composition obtained by mixing a silicate-containing n-cyanic acid ester-based resin, a water curing agent, and calcium-silicate powder at a weight ratio of 1:0.5:1 (Example 1), and a composition obtained by mixing a weight ratio of 1:0.5:1.5 (Example 2 ) were prepared, respectively, and then applied to the base plate to prepare a specimen having an average thickness of 3.5 mm of the flooring material.
[비교예][Comparative example]
비교를 위하여 대한민국 등록특허공보 10-1067471호에 따라 제조된 하이브리드 분체와 수경화제를 1:0.5의 중량비로 혼합하여 바탕 콘크리트에 1차 도포하고 시안산 에스테르계 중합수지 및 수경화제를 2차 코팅하여 제조한 시험체를 준비하였다(비교예 1). 또한, 종래의 휘발성 유기용제를 사용하는 에폭시 수지계 바닥재를 바탕 콘크리트에 시방서에 따라 코팅하여 제조된 시험체(비교예 2) 및 종래의 휘발성 유기용제를 사용하는 우레탄 수지계 바닥재를 시방서에 따라 코팅하여 제조된 시험체(비교예 3)을 준비하였다.For comparison, the hybrid powder prepared according to Korean Patent Registration No. 10-1067471 and the hydraulic curing agent were mixed at a weight ratio of 1:0.5, applied first to the base concrete, and then the cyanate ester-based polymer resin and the hydraulic curing agent were secondly coated. A prepared test body was prepared (Comparative Example 1). In addition, a test specimen (Comparative Example 2) prepared by coating an epoxy resin-based flooring material using a conventional volatile organic solvent on the base concrete according to the specifications and a urethane resin-based flooring material using a conventional volatile organic solvent prepared by coating according to the specifications A test body (Comparative Example 3) was prepared.
[바닥재 물성평가][Floor material property evaluation]
실시예 및 비교예에 따른 시험체에 대하여 KS F 4937[:2019(주차장 바닥용 표면 마감재) 시험 항목인 내충격 성능, 부착 성능, 윤하중 저항 성능, 수밀 성능 및 오염 물질 방출 시험을 실시하였다. KS F 4937 시험규격에 따른 시험 항목 및 합격 기준은 표 1과 같다.KS F 4937 [: 2019 (Surface Finishing Materials for Parking Lot Floors) test items, impact resistance performance, adhesion performance, wheel load resistance performance, water tightness performance and contaminant release tests were conducted on the test specimens according to Examples and Comparative Examples. Table 1 shows the test items and acceptance criteria according to the KS F 4937 test standard.
(300㎏, 80,000회)Wheel load resistance performance
(300kg, 80,000 times)
(㎎/㎡·h)pollutant release
(mg/m² h)
실시예 및 비교예의 시험체에 대한 KS F 4937[:2019에 따른 시험 결과는 하기 표 2와 같다.Test results according to KS F 4937 [: 2019 for the test specimens of Examples and Comparative Examples are shown in Table 2 below.
성능Yun Ha-joong
Performance
표 2의 시험결과를 살펴보면, 실시예 1, 2에 따른 바닥재 조성물은 KS F 4937 시험기준을 모두 충족하는 것으로 나타났다. 특히, 산업 부산물을 원료로 사용하면서도 종래기술에 따른 바닥재 조성물(비교예 1)과 동등한 정도의 물성을 나타내는 것을 확인하였다. 또한, 종래의 에폭시 수지계(비교예 2)나 우레탄 수지계(비교예 3)와 비교하여도 물성이 우수한 것을 확인할 수 있었다.Looking at the test results in Table 2, it was found that the flooring compositions according to Examples 1 and 2 met all of the KS F 4937 test standards. In particular, while using industrial by-products as raw materials, it was confirmed that they exhibit physical properties equivalent to those of the conventional flooring composition (Comparative Example 1). In addition, it was confirmed that the physical properties were excellent compared to conventional epoxy resin systems (Comparative Example 2) or urethane resin systems (Comparative Example 3).
또한, 실시예 1에 따른 바닥재 조성물을 이용하여 시험체를 제조하고 이를 한국화학융합시험연구원에 의뢰하여 준불연 시험을 실시하였다. 시험체는 3㎜ 두께의 변성 우레탄 표면에 20㎜의 바닥재를 도포한 것을 사용하였으며, 국토교통부고시 제2020-263호(건축물 마감재료의 난연성능 및 화재 확산 방지구조 기준)에 따라 시험평가를 실시하였다. 상기 기준을 충족시키기 위해서는 총방출열량이 8MJ/㎡ 이하, 열방출율이 200kW/㎡를 연속하여 초과한 시간이 10초 이하, 가스유해성 시험에 따른 평균행동정지시간이 9분 이상인 조건을 충족해야 하며, 시험 후 시험체의 심재 균열, 구멍 및 용융이 없어야 한다.In addition, a test body was prepared using the flooring composition according to Example 1, and a semi-incombustible test was conducted by requesting it to the Korea Institute of Chemical Convergence Testing. The test specimen was used with a 20 mm layer of flooring applied to a 3 mm thick modified urethane surface, and a test evaluation was conducted in accordance with Ministry of Land, Infrastructure and Transport Notice No. 2020-263 (Flame retardant performance of building finishing materials and fire spread prevention structure standards) . In order to meet the above criteria, the total heat release rate is 8 MJ/㎡ or less, the heat release rate continuously exceeds 200 kW/㎡ for 10 seconds or less, and the average action suspension time according to the gas hazard test is 9 minutes or more. , there shall be no cracks, holes and melting of the core of the specimen after the test.
시험 결과 총방출열량은 0.1MJ/㎡, 열방출율이 200kW/㎡를 연속하여 초과한 시간이 0초, 가스유해성 시험에 따른 평균행동정지시간이 13분 42초이며, 시험 후 시험체의 검사에서 이상이 없는 것으로 나타나 준불연 성능을 충족하는 것으로 나타났다.As a result of the test, the total amount of heat released was 0.1MJ/㎡, the time when the heat release rate continuously exceeded 200kW/㎡ was 0 seconds, and the average suspension time according to the gas hazard test was 13 minutes and 42 seconds. It was found that there was no , and it was found to satisfy the semi-incombustible performance.
또한, 실시예 1의 바닥재 조성물 및 비교예 2의 바닥재 조성물을 이용하여 제조된 시험체에 화염을 분사한 후의 상태를 관찰하였다. 그 결과 도 1에서와 같이 실시예 1의 바닥재 조성물을 적용한 시험체의 경우 비교예 2와 달리 화염에 의한 화재가 발생하지 않고 화염 분사를 멈추면 불꽃이 사라지는 것으로 나타났다. 이에 반해 비교예 2의 바닥재 조성물을 적용한 시험체의 경우 화염 분사 후 분사를 멈추면 불이 붙은 상태가 되었으며 불을 끈 후의 상태를 관찰하면 표면이 심하게 탄 것을 확인할 수 있었다.In addition, the state after spraying the flame on the test body prepared using the flooring composition of Example 1 and the flooring composition of Comparative Example 2 was observed. As a result, in the case of the test specimen to which the flooring composition of Example 1 was applied, as shown in FIG. 1, unlike Comparative Example 2, it was found that the flame disappeared when the flame injection was stopped without a fire caused by the flame. On the other hand, in the case of the test specimen to which the flooring composition of Comparative Example 2 was applied, when the spraying was stopped after the flame spraying, it was in a state of fire, and when the state after turning off the fire was observed, it was confirmed that the surface was severely burned.
또한, 상기 화염 분사에 의한 시험을 통해 양호한 결과를 나타낸 실시예 1의 바닥재 조성물로 제조된 시험체에 대해 한국화학융합시험연구원에 시험을 의뢰한 결과 도 2에서와 같이 준불연 특성을 모두 충족하는 것으로 나타났다.In addition, as a result of requesting a test to the Korea Testing & Research Institute for the test body made of the flooring composition of Example 1, which showed good results through the flame spray test, it was found to satisfy all of the semi-incombustible characteristics as shown in FIG. appear.
본 발명은 상술한 바와 같이 바람직한 실시예를 들어 설명하였으나, 상기 실시예에 한정되지 아니하며 본 발명의 정신을 벗어나지 않는 범위 내에서 당해 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 다양한 변형과 변경이 가능하다. 그러한 변형예 및 변경예는 본 발명과 첨부된 특허청구범위의 범위 내에 속하는 것으로 보아야 한다.Although the present invention has been described with preferred embodiments as described above, it is not limited to the above embodiments, and various modifications and modifications can be made by those skilled in the art within the scope of not departing from the spirit of the present invention. Change is possible. Such modifications and variations are intended to fall within the scope of this invention and the appended claims.
Claims (5)
상기 n-시안산 에스테르계 수지는 규산염 함유 n-시안산 에스테르계 수지이며,
상기 칼슘-규산염 분체는 배연탈황석고 및 황토를 포함하는 것을 특징으로 하는 준불연 친환경 바닥재 조성물.
A semi-incombustible eco-friendly flooring composition composed of n-cyanic acid ester-based resin, a water curing agent and calcium-silicate powder,
The n-cyanic acid ester-based resin is a silicate-containing n-cyanic acid ester-based resin,
The calcium-silicate powder is a semi-incombustible eco-friendly flooring composition, characterized in that it comprises flue gas desulfurization gypsum and loess.
상기 규산염 함유 n-시안산 에스테르계 수지는 시안산 메틸(CH3OC≡N), 시안산 에틸(C2H5OC≡N), 시안산 이소프로필(i-C3H7OC≡N), 시안산 이소부틸(i-C4H9OC≡N) 및 시안산 페닐(C6H5OC≡N))에서 선택되는 어느 하나의 n-시안산 에스테르계 단량체를 산 촉매 하에서 중합 반응하여 중합수지를 제조하고, 상기 중합수지 100 중량부에 대하여 고형분(SiO2)의 함량이 부산물의 5 중량% 미만인 저순도 테트라오르소실리케이트에 산 촉매를 가하여 가수분해하여 수득된 규산염 수용액 100 내지 200 중량부를 혼합하여 제조되는 것을 특징으로 하는 준불연 친환경 바닥재 조성물.
The method of claim 1,
The silicate-containing n-cyanate ester-based resin is methyl cyanate (CH 3 OC≡N), ethyl cyanate (C 2 H 5 OC≡N), isopropyl cyanate (iC 3 H 7 OC≡N), cyanide A polymer resin is prepared by polymerization of any one n-cyanic acid ester-based monomer selected from isobutyl acid (iC 4 H 9 OC≡N) and phenyl cyanate (C 6 H 5 OC≡N) under an acid catalyst. and mixing 100 to 200 parts by weight of an aqueous silicate solution obtained by hydrolysis by adding an acid catalyst to low-purity tetraorthosilicate having a solid content (SiO 2 ) of less than 5% by weight of by-products based on 100 parts by weight of the polymer resin. Semi-incombustible eco-friendly flooring composition, characterized in that the.
상기 수경화제는 글리콜산(glycolic acid) 및 다가 알코올을 함유하는 수용액으로서, 상기 다가 알코올은 1,4-부틴디올, 에틸렌글리콜, 프로필렌글리콜, 디에틸렌글리콜 및 폴리테트라메틸렌글리콜 중에서 선택되는 어느 하나인 것을 특징으로 하는 준불연 친환경 바닥재 조성물.
The method of claim 1,
The hydraulic curing agent is an aqueous solution containing glycolic acid and a polyhydric alcohol, wherein the polyhydric alcohol is any one selected from 1,4-butyndiol, ethylene glycol, propylene glycol, diethylene glycol and polytetramethylene glycol. Semi-incombustible eco-friendly flooring composition, characterized in that.
상기 배연탈황석고는 산화칼슘(CaO)을 30 내지 50 질량% 함유하는 것을 특징으로 하는 준불연 친환경 바닥재 조성물.
The method of claim 1,
The flue gas desulfurization gypsum is a semi-incombustible eco-friendly flooring composition, characterized in that it contains 30 to 50% by mass of calcium oxide (CaO).
상기 준불연 친환경 바닥재 조성물은 n-시안산 에스테르계 수지 100 중량부에 대하여, 수경화제 50 내지 100 중량부 및 칼슘-규산염 분체 100 내지 150 중량부로 이루어지는 것을 특징으로 하는 준불연 친환경 바닥재 조성물.The method of claim 1,
The semi-nonflammable eco-friendly flooring composition is a semi-nonflammable eco-friendly flooring composition, characterized in that consisting of 50 to 100 parts by weight of a water curing agent and 100 to 150 parts by weight of calcium-silicate powder based on 100 parts by weight of n-cyanic acid ester-based resin.
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| KR101067471B1 (en) * | 2011-04-14 | 2011-09-27 | 주식회사 포스코건설 | Eco-friendly bottom material compositions composed water soluble n-cyanic acid ester polymer resin and hybrid divided complex, and construction method using this |
| KR20220037001A (en) * | 2020-09-16 | 2022-03-24 | 에코리엔트샤인 (주) | Environment-friendly composition for phosphorescent stone materials having improved durability and constructing method for road flooring using the same |
| KR102396556B1 (en) * | 2022-01-11 | 2022-05-13 | 계룡건설산업 주식회사 | Eco-friendly flooring material composition comprising modified urea resin compostion and desulfurized gypsum |
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| KR101067471B1 (en) * | 2011-04-14 | 2011-09-27 | 주식회사 포스코건설 | Eco-friendly bottom material compositions composed water soluble n-cyanic acid ester polymer resin and hybrid divided complex, and construction method using this |
| KR20220037001A (en) * | 2020-09-16 | 2022-03-24 | 에코리엔트샤인 (주) | Environment-friendly composition for phosphorescent stone materials having improved durability and constructing method for road flooring using the same |
| KR102396556B1 (en) * | 2022-01-11 | 2022-05-13 | 계룡건설산업 주식회사 | Eco-friendly flooring material composition comprising modified urea resin compostion and desulfurized gypsum |
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