KR102603122B1 - Cellulose fiber based eco-friendly composites having fire retardant and sound absorbing - Google Patents
Cellulose fiber based eco-friendly composites having fire retardant and sound absorbing Download PDFInfo
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- KR102603122B1 KR102603122B1 KR1020210138971A KR20210138971A KR102603122B1 KR 102603122 B1 KR102603122 B1 KR 102603122B1 KR 1020210138971 A KR1020210138971 A KR 1020210138971A KR 20210138971 A KR20210138971 A KR 20210138971A KR 102603122 B1 KR102603122 B1 KR 102603122B1
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- flame retardant
- weight
- retardant composition
- cellulose fibers
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 95
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 97
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 20
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 20
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 19
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 19
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 19
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 19
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 19
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004327 boric acid Substances 0.000 claims abstract description 18
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims description 15
- 229920001038 ethylene copolymer Polymers 0.000 claims description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 11
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 238000002845 discoloration Methods 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 37
- 230000000052 comparative effect Effects 0.000 description 75
- 238000011156 evaluation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000004566 building material Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229920002522 Wood fibre Polymers 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000002025 wood fiber Substances 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- VWVRASTUFJRTHW-UHFFFAOYSA-N 2-[3-(azetidin-3-yloxy)-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound O=C(CN1C=C(C(OC2CNC2)=N1)C1=CN=C(NC2CC3=C(C2)C=CC=C3)N=C1)N1CCC2=C(C1)N=NN2 VWVRASTUFJRTHW-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
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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
- 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/67—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with cyanogen or compounds thereof, e.g. with cyanhydric acid, cyanic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid or their salts, or with cyanamides; with carbamic acid or its salts
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
- D06M11/71—Salts of phosphoric acids
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
- D06M11/82—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
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Abstract
본 발명은 셀룰로오스 섬유로 형성된 기재 시트; 및 상기 기재 시트에 함침되되, 황산 암모늄(Diazanium sulfate), 디시안디아마이드(Dicyandiamide), 펜타에리트리톨(Pentaerythritol), 인산 암모늄(Ammonium phosphate), 붕산(Boric acid) 및 바인더를 포함하는 셀룰로오스 섬유용 난연 조성물;을 포함함에 따라, 셀룰로오스 섬유로 형성된 기재 시트와 난연 조성물 간의 접착성이 좋으면서도 난연성 및 흡음성이 우수한 친환경 복합소재에 관한 것이다.The present invention relates to a base sheet formed of cellulose fibers; and a flame retardant for cellulose fibers impregnated into the base sheet and containing ammonium sulfate, Dicyandiamide, Pentaerythritol, Ammonium phosphate, Boric acid, and a binder. The present invention relates to an eco-friendly composite material that has good adhesion between a base sheet made of cellulose fibers and a flame retardant composition and has excellent flame retardancy and sound absorption.
Description
본 발명은 난연성 및 흡음성이 향상된 셀룰로오스 섬유 기반의 친환경 복합소재에 관한 것이다.The present invention relates to an eco-friendly composite material based on cellulose fibers with improved flame retardancy and sound absorption.
구체적으로, 본 발명은 셀룰로오스 섬유를 기반으로 하는 복합소재로서, 특정한 난연 조성물이 적용됨에 따라, 우수한 난연성 및 흡음성을 구현할 수 있는, 친환경 건축재, 자동차 내장재, 포장재 및/또는 기계 단열재에 관한 것이다.Specifically, the present invention relates to an eco-friendly building material, automobile interior material, packaging material, and/or mechanical insulation material, which is a composite material based on cellulose fibers and can realize excellent flame retardancy and sound absorption when a specific flame retardant composition is applied.
일반적으로 단열, 흡음 등의 효능을 가지는 건축재, 자동차 내장재 등의 복합소재로서, 암면(Mineral wool) 이나, 유리섬유(Glass Wool) 등이 주로 사용되고 있으나, 암면 또는 유리섬유의 경우, 제조 과정 및 시공 과정에서, 환경에 유해하고, 인체에 안전하지 못한 성분들이 방출됨에 따라, 이의 사용이 배제되고 있는 실정이다.In general, as a composite material for building materials and automobile interior materials that have effects such as insulation and sound absorption, mineral wool or glass wool are mainly used. However, in the case of rock wool or glass fiber, the manufacturing process and construction In the process, ingredients that are harmful to the environment and unsafe to the human body are released, so their use is being excluded.
이에 따라, 최근에는 목재섬유에서 수득된 천연 셀룰로오스 섬유를 건축재, 자동차 내장재 등을 비롯한 복합소재로서 사용하고자 하는 시도들이 활발하다. 일례로, 대한민국 등록특허 제10-2278958호에서는 친수성 실리카 에어로겔 입자 및 나노 셀룰로오스 섬유를 포함하여, 단열재, 방음재 등으로 활용될 수 있는 복합소재에 대해 개시하고 있다.Accordingly, there have been active recent attempts to use natural cellulose fibers obtained from wood fibers as composite materials, including building materials and automobile interior materials. For example, Republic of Korea Patent No. 10-2278958 discloses a composite material including hydrophilic silica airgel particles and nanocellulose fibers that can be used as insulation and soundproofing materials.
한편, 상기와 같은 복합소재에는 단열, 흡음 등의 특성 이외에 불에 쉽게 타지 않는 난연성이 필수적으로 요구되고 있으나, 목재섬유에서 유래된 천연 셀룰로오스 섬유의 경우, 불에 노출되면 유기 성분이 탄화되어 쉽게 부서지는 문제가 있었다. 이에 따라, 천연 셀룰로오스 섬유를 이용한 복합소재에는 난연성을 위한 별도의 처리가 필수적인 상황이다. On the other hand, in addition to properties such as insulation and sound absorption, composite materials such as the above essentially require flame retardancy so that they do not burn easily. However, in the case of natural cellulose fibers derived from wood fibers, when exposed to fire, the organic components are carbonized and easily broken. There was a problem with losing. Accordingly, separate treatment for flame retardancy is essential for composite materials using natural cellulose fibers.
그러나, 천연 셀룰로오스 섬유로 형성된 시트는, 내부 구조가 복잡하고, 공극의 위치나 크기가 불균일하여, 난연 조성물이 균일하게 함침되지 않거나, 난연 조성물이 시트에 충분히 접착되지 못하고 쉽게 떨어져 나가는 문제가 있었다.However, sheets made of natural cellulose fibers have a complex internal structure and uneven positions and sizes of pores, so there is a problem that the flame retardant composition is not uniformly impregnated or the flame retardant composition is not sufficiently adhered to the sheet and easily falls off.
따라서, 천연 셀룰로오스 섬유를 기반으로 하는 기재 시트에 균일하게 침투되어 충분히 접착 및 지지되면서도 우수한 난연성 및 흡음성을 구현할 수 있는 난연 조성물을 이용한, 복합소재에 대한 개발이 요구되고 있다.Therefore, there is a need for the development of a composite material using a flame retardant composition that can uniformly penetrate a base sheet based on natural cellulose fibers and provide sufficient adhesion and support while providing excellent flame retardancy and sound absorption.
본 발명의 목적은 황산 암모늄(Diazanium sulfate), 디시안디아마이드(Dicyandiamide), 펜타에리트리톨(Pentaerythritol), 인산 암모늄(Ammonium phosphate), 붕산(Boric acid) 및 바인더를 포함하는 셀룰로오스 섬유용 난연 조성물을 셀룰로오스 섬유로 형성된 기재 시트에 함침시켜 형성되는 것으로, 난연성 및 흡음성이 우수한, 친환경 복합소재를 제공하는 데에 있다.The object of the present invention is to provide a flame retardant composition for cellulose fibers containing ammonium sulfate, dicyandiamide, pentaerythritol, ammonium phosphate, boric acid and a binder. The purpose is to provide an eco-friendly composite material that is formed by impregnating a base sheet formed of fibers and has excellent flame retardancy and sound absorption.
본 발명의 목적은 상기된 바와 같은 기술적 과제로 한정되지 않으며, 이하의 설명으로부터 또 다른 기술적 과제가 도출될 수 있다. The purpose of the present invention is not limited to the technical problems described above, and other technical problems may be derived from the following description.
상기 목적을 달성하기 위하여, 본 발명은 셀룰로오스 섬유로 형성된 기재 시트; 및 상기 기재 시트에 함침된 셀룰로오스 섬유용 난연 조성물;을 포함하되, 상기 셀룰로오스 섬유용 난연 조성물은 황산 암모늄(Diazanium sulfate), 디시안디아마이드(Dicyandiamide), 펜타에리트리톨(Pentaerythritol), 인산 암모늄(Ammonium phosphate), 붕산(Boric acid) 및 바인더를 포함하는 셀룰로오스 섬유 기반의 친환경 복합소재를 제공한다.In order to achieve the above object, the present invention provides a base sheet formed of cellulose fibers; and a flame retardant composition for cellulose fibers impregnated in the base sheet, wherein the flame retardant composition for cellulose fibers includes ammonium sulfate, dicyandiamide, pentaerythritol, and ammonium phosphate. ), provides an eco-friendly composite material based on cellulose fibers containing boric acid and a binder.
상기 셀룰로오스 섬유용 난연 조성물은 상기 셀룰로오스 섬유용 난연 조성물 총 중량 기준으로 황산 암모늄 10 ~ 20 중량%, 디시안디아마이드(Dicyandiamide) 7 ~ 13 중량%, 펜타에리트리톨 1 ~ 8 중량%, 인산 암모늄 15 ~ 25 중량%, 붕산 7 ~ 15 중량% 및 바인더 3 ~ 8 중량%를 포함할 수 있다.The flame retardant composition for cellulose fibers contains 10 to 20% by weight of ammonium sulfate, 7 to 13% by weight of dicyandiamide, 1 to 8% by weight of pentaerythritol, and 15 to 15% by weight of ammonium phosphate, based on the total weight of the flame retardant composition for cellulose fibers. It may contain 25% by weight, 7 to 15% by weight of boric acid, and 3 to 8% by weight of binder.
상기 바인더는 비닐아세테이트-에틸렌 공중합체(Ethylene Vinyl Acetate) 및 수용성 스티렌 부타디엔 고무(Styrene Butadiene Rubber)로 이루어진 군에서 선택되는 하나 이상을 포함할 수 있다.The binder may include one or more selected from the group consisting of vinyl acetate-ethylene copolymer (Ethylene Vinyl Acetate) and water-soluble styrene butadiene rubber.
상기 바인더는 비닐아세테이트-에틸렌 공중합체(Ethylene Vinyl Acetate) 및 수용성 스티렌 부타디엔 고무(Styrene Butadiene Rubber)를 1 : 5 ~ 15 의 중량비로 포함할 수 있다.The binder may include vinyl acetate-ethylene copolymer (Ethylene Vinyl Acetate) and water-soluble styrene butadiene rubber at a weight ratio of 1:5 to 15.
상기 난연 조성물은 분산제, 계면활성제, 안료, 소포제, 산화 방지제, 변색 방지제, 가소제 및 용매로 이루어진 군에서 선택되는 하나 이상을 더 포함할 수 있다.The flame retardant composition may further include one or more selected from the group consisting of dispersants, surfactants, pigments, anti-foaming agents, antioxidants, discoloration inhibitors, plasticizers, and solvents.
본 발명의 복합소재는 셀룰로오스 섬유로 형성된 기재 시트에, 황산 암모늄(Diazanium sulfate), 디시안디아마이드(Dicyandiamide), 펜타에리트리톨(Pentaerythritol), 인산 암모늄(Ammonium phosphate), 붕산(Boric acid) 및 바인더를 포함하는 난연 조성물이 함침되어 형성되는 것으로, 난연성 및 흡음성이 우수할 수 있다.The composite material of the present invention is a base sheet formed of cellulose fibers, containing ammonium sulfate, dicyandiamide, pentaerythritol, ammonium phosphate, boric acid, and a binder. It is formed by impregnating a flame retardant composition containing it, and may have excellent flame retardancy and sound absorption.
구체적으로, 셀룰로오스 섬유로 형성된 기재 시트에, 상기 난연 조성물이 균일하게 침투 및 지지됨으로써, 우수한 난연성 및 흡음성을 구현할 수 있다. 뿐만 아니라, 셀룰로오스 섬유와 난연 조성물 간의 접착력이 향상되어, 난연성 및 흡음성의 지속성이 우수할 수 있다.Specifically, by uniformly penetrating and supporting the flame retardant composition in a base sheet formed of cellulose fibers, excellent flame retardancy and sound absorption can be achieved. In addition, the adhesion between cellulose fibers and the flame retardant composition is improved, and the sustainability of flame retardancy and sound absorption can be excellent.
도 1은 실시예 3에 따르는 복합소재의 난연성 평가 결과를 도시한 도면이다.
도 2는 비교예 1에 따르는 복합소재의 난연성 평가 결과를 도시한 도면이다.
도 3은 비교예 9에 따르는 복합소재의 난연성 평가 결과를 도시한 도면이다.
도 4는 비교예 12에 따르는 복합소재의 난연성 평가 결과를 도시한 도면이다.Figure 1 is a diagram showing the flame retardancy evaluation results of the composite material according to Example 3.
Figure 2 is a diagram showing the flame retardancy evaluation results of the composite material according to Comparative Example 1.
Figure 3 is a diagram showing the flame retardancy evaluation results of the composite material according to Comparative Example 9.
Figure 4 is a diagram showing the flame retardancy evaluation results of the composite material according to Comparative Example 12.
아래에서는 첨부한 도면을 참조하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예를 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 그리고 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였다.Below, with reference to the attached drawings, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein. In order to clearly explain the present invention in the drawings, parts unrelated to the description are omitted.
본 발명의 명세서 및 청구범위에 사용된 용어 또는 단어는 통상적이거나 사전적인 의미로 한정 해석되지 아니하며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the specification and claims of the present invention are not to be construed as limited to their ordinary or dictionary meanings, and the inventor may appropriately define the concept of terms to explain his or her invention in the best way. It must be interpreted as meaning and concept consistent with the technical idea of the present invention based on principles.
본 발명의 명세서 전체에 있어서, 어떤 부분이 어떤 구성 요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다. Throughout the specification of the present invention, when a part is said to "include" a certain component, this means that it does not exclude other components but may further include other components, unless specifically stated to the contrary. .
본 발명의 명세서 전체에 있어서, "A 및/또는 B"는, A 또는 B, 또는 A 및 B를 의미한다.Throughout the specification of the present invention, “A and/or B” means A or B, or A and B.
이하에서 본 발명을 구체적으로 설명하였으나, 본 발명이 이에 제한되는 것은 아니다.Although the present invention is described in detail below, the present invention is not limited thereto.
본 발명에서는 난연성 및 흡음성이 향상된 셀룰로오스 섬유 기반의 친환경 복합소재를 제공한다.The present invention provides an eco-friendly composite material based on cellulose fibers with improved flame retardancy and sound absorption.
본 발명의 일 실시예에서는 셀룰로오스 섬유로 형성된 기재 시트; 및 상기 기재 시트에 함침된 셀룰로오스 섬유용 난연 조성물;을 포함하되, 상기 셀룰로오스 섬유용 난연 조성물은 황산 암모늄(Diazanium sulfate), 디시안디아마이드(Dicyandiamide), 펜타에리트리톨(Pentaerythritol), 인산 암모늄(Ammonium phosphate), 붕산(Boric acid) 및 바인더를 포함하는, 난연성 및 흡음성이 향상된 셀룰로오스 섬유 기반의 친환경 복합소재를 제공한다. 구체적으로, 본 실시예의 복합소재는 셀룰로오스 섬유로 형성된 기재 시트에, 특정 조성의 난연 조성물을 함침 및 경화시켜 형성된 것 일 수 있다.In one embodiment of the present invention, a base sheet formed of cellulose fibers; and a flame retardant composition for cellulose fibers impregnated in the base sheet, wherein the flame retardant composition for cellulose fibers includes ammonium sulfate, dicyandiamide, pentaerythritol, and ammonium phosphate. ), boric acid, and a binder, and provide an eco-friendly composite material based on cellulose fibers with improved flame retardancy and sound absorption. Specifically, the composite material of this example may be formed by impregnating and curing a flame retardant composition of a specific composition into a base sheet formed of cellulose fibers.
본 실시예에 따르면, 셀룰로오스 섬유로 형성된 기재 시트 내에 상기 난연 조성물이 균일하게 침투 및 지지됨에 따라, 셀룰로오스 섬유와 난연 조성물 간의 부착성이 향상될 수 있다. 이에 따라, 본 실시예의 복합소재는 난연성 및 이의 지속성이 우수할 수 있다.According to this embodiment, as the flame retardant composition is uniformly penetrated and supported within the base sheet formed of cellulose fibers, the adhesion between the cellulose fibers and the flame retardant composition may be improved. Accordingly, the composite material of this embodiment may have excellent flame retardancy and sustainability.
또한, 본 실시예에 따라, 셀룰로오스 섬유로 형성된 기재 시트 내에 상기 난연 조성물이 균일하게 침투 및 지지됨에 따라, 전반적인 물성 및 흡음성이 향상될 수 있다.Additionally, according to this embodiment, as the flame retardant composition is uniformly penetrated and supported within the base sheet formed of cellulose fibers, the overall physical properties and sound absorption properties may be improved.
본 실시예의 복합소재는 셀룰로오스 섬유로 형성된 기재 시트를 포함한다. 구체적으로, 본 실시예의 셀룰로오스 섬유로 형성된 기재 시트는 셀룰로오스 섬유를 주재료로 하는 모든 형태의 시트를 의미할 수 있다. 이때, 상기 셀룰로오스 섬유는 천연 셀룰로오스 섬유로서, 목재 섬유를 의미할 수 있다.The composite material of this example includes a base sheet formed of cellulose fibers. Specifically, the base sheet formed of cellulose fibers of this embodiment may refer to any type of sheet that uses cellulose fibers as the main material. At this time, the cellulose fiber is a natural cellulose fiber and may mean wood fiber.
본 실시예의 셀룰로오스 섬유로 형성된 기재 시트는, 셀룰로오스 섬유로 형성된 기재 시트가 단층으로 형성되거나, 다층으로 적층된 것일 수 있다.The base sheet made of cellulose fibers of this embodiment may be a single layer or a multi-layered base sheet made of cellulose fibers.
본 실시예의 셀룰로오스 섬유로 형성된 기재 시트는 두께가 1 ㎛ ~ 100 mm, 구체적으로는 0.1 ~ 100 mm, 더 구체적으로는 1 ~ 100 mm 로 형성될 수 있으나, 이에 제한되지 않는다.The base sheet made of cellulose fibers of this embodiment may have a thickness of 1 μm to 100 mm, specifically 0.1 to 100 mm, and more specifically 1 to 100 mm, but is not limited thereto.
본 실시예의 셀룰로오스 섬유로 형성된 기재 시트에는 황산 암모늄(Diazanium sulfate), 디시안디아마이드(Dicyandiamide), 펜타에리트리톨(Pentaerythritol), 인산 암모늄(Ammonium phosphate), 붕산(Boric acid) 및 바인더를 포함하는 난연 조성물이 함침 및 경화 되어, 우수한 난연성 및 흡음성을 구현한다.The base sheet formed of cellulose fibers of this embodiment includes a flame retardant composition containing ammonium sulfate, dicyandiamide, pentaerythritol, ammonium phosphate, boric acid, and a binder. This impregnation and curing provides excellent flame retardancy and sound absorption.
본 실시예의 난연 조성물은 황산 암모늄, 인산 암모늄을 모두 포함하며, 상기 두 성분은 80 ~ 280 ℃ 의 열에 노출되어, 암모니아 가스와 물을 동시에 배출하면서 탈수 탄화 작용함으로써, 불의 소화를 도움에 따라, 난연 특성은 더욱 향상될 수 있다. 특히, 본 실시예의 난연 조성물은 열에 노출되어도 가연성 가스에 해당하는 일산화탄소를 거의 배출하지 않음으로써, 연소 확대 방지, 일산화탄소 흡인에 따른 중독 등의 문제를 방지할 수 있다. 즉, 본 실시예의 난연 조성물은 일산화탄소 등의 유독 가스 생성을 최소화함으로써, 친환경적일 수 있다.The flame retardant composition of this embodiment contains both ammonium sulfate and ammonium phosphate, and the two components are exposed to heat of 80 to 280 ° C. and perform a dehydration carbonization effect while simultaneously releasing ammonia gas and water, thereby helping to extinguish the fire, thereby providing a flame retardant. The characteristics can be further improved. In particular, the flame retardant composition of this embodiment hardly emits carbon monoxide, which is a combustible gas, even when exposed to heat, thereby preventing problems such as combustion expansion and poisoning due to carbon monoxide inhalation. That is, the flame retardant composition of this embodiment can be environmentally friendly by minimizing the generation of toxic gases such as carbon monoxide.
이하에서는, 상기 난연 조성물에 대해 상세히 설명하도록 하겠다.Below, the flame retardant composition will be described in detail.
본 실시예의 난연 조성물은 황산 암모늄을 포함하되, 상기 난연 조성물 총 중량 기준으로 황산 암모늄을 10 ~ 20 중량%, 구체적으로는 15 ~ 20 중량%, 더 구체적으로는 17 ~ 18 중량%로 포함할 수 있다. 특히, 본 실시예의 난연 조성물이 황산 암모늄을 포함하되, 이를 17 ~ 18 중량%로 포함할 때, 기재 시트와 난연 조성물 간의 접착성이 우수하면서도 난연성 및 흡음성이 향상된, 복합소재를 제공할 수 있다.The flame retardant composition of this embodiment includes ammonium sulfate, and may include 10 to 20 wt% of ammonium sulfate, specifically 15 to 20 wt%, and more specifically 17 to 18 wt%, based on the total weight of the flame retardant composition. there is. In particular, when the flame retardant composition of this embodiment includes ammonium sulfate in an amount of 17 to 18% by weight, a composite material with excellent adhesion between the base sheet and the flame retardant composition and improved flame retardancy and sound absorption can be provided.
만약, 본 실시예의 난연 조성물이 총 중량 기준으로 상기 황산 암모늄을 10 중량% 미만으로 포함할 경우에는, 상기 황산 암모늄을 10 ~ 20 중량%로 포함하는 경우 보다, 난연성 및 흡음성이 저하될 수 있다. 반면, 본 실시예의 난연 조성물이 총 중량 기준으로 상기 황산 암모늄을 20 중량% 초과로 포함할 경우에는, 상기 황산 암모늄을 10 ~ 20 중량%로 포함하는 경우 보다, 기재 시트와 난연 조성물 간의 접착성이 저하되어, 난연성 및 흡음성 또한 저하될 수 있다.If the flame retardant composition of this example contains less than 10% by weight of ammonium sulfate based on the total weight, flame retardancy and sound absorption may be lowered than when it contains 10 to 20% by weight of ammonium sulfate. On the other hand, when the flame retardant composition of this example contains more than 20% by weight of ammonium sulfate based on the total weight, the adhesion between the base sheet and the flame retardant composition is lower than when it contains 10 to 20% by weight of ammonium sulfate. As a result, flame retardancy and sound absorption may also be reduced.
본 실시예의 난연 조성물은 디시안디아마이드를 포함하되, 상기 난연 조성물 총 중량 기준으로 디시안디아마이드를 7 ~ 13 중량%, 구체적으로는 8 ~ 12 중량%, 더 구체적으로는 9 ~ 12 중량%로 포함할 수 있다. 특히, 본 실시예의 난연 조성물이 디시안디아마이드를 9 ~ 12 중량%로 포함할 때, 기재 시트와 난연 조성물 간의 접착성이 우수하면서도 난연성 및 흡음성이 향상된, 복합소재를 제공할 수 있다. The flame retardant composition of this embodiment includes dicyandiamide, and includes 7 to 13 wt% of dicyandiamide, specifically 8 to 12 wt%, more specifically 9 to 12 wt%, based on the total weight of the flame retardant composition. can do. In particular, when the flame retardant composition of this example contains 9 to 12% by weight of dicyandiamide, a composite material having excellent adhesion between the base sheet and the flame retardant composition and improved flame retardancy and sound absorption can be provided.
만약, 본 실시예의 난연 조성물이 총 중량 기준으로 디시안디아마이드를 7 중량% 미만으로 포함할 경우에는, 상기 디시안디아마이드를 7 ~ 13 중량%로 포함하는 경우 보다, 난연성이 저하될 수 있다. 반면, 본 실시예의 난연 조성물이 총 중량 기준으로 상기 디시안디아마이드를 13 중량% 초과로 포함할 경우에는, 상기 디시안디아마이드를 7 ~ 13 중량%로 포함하는 경우 보다, 기재 시트와 난연 조성물 간의 접착성이 저하되며, 난연성 및 흡음성 또한 저하될 수 있다.If the flame retardant composition of this example contains less than 7% by weight of dicyandiamide based on the total weight, the flame retardancy may be lowered than when it contains 7 to 13% by weight of dicyandiamide. On the other hand, when the flame retardant composition of this example contains more than 13% by weight of dicyandiamide based on the total weight, the adhesion between the base sheet and the flame retardant composition is greater than when the flame retardant composition of the present example contains 7 to 13% by weight of dicyandiamide. Performance decreases, and flame retardancy and sound absorption may also decrease.
본 실시예의 난연 조성물은 펜타에리트리톨을 포함하되, 상기 난연 조성물 총 중량 기준으로 펜타에리트리톨을 1 ~ 8 중량%, 구체적으로는 2 ~ 7 중량%, 더 구체적으로는 3 ~ 6 중량%로 포함할 수 있다. 특히, 본 실시예의 난연 조성물이 펜타에리트리톨을 3 ~ 6 중량%로 포함할 때, 기재 시트와 난연 조성물 간의 접착성이 우수하면서도 난연성 및 흡음성이 향상된, 복합소재를 제공할 수 있다.The flame retardant composition of this embodiment includes pentaerythritol, and contains 1 to 8 wt% of pentaerythritol, specifically 2 to 7 wt%, and more specifically 3 to 6 wt%, based on the total weight of the flame retardant composition. can do. In particular, when the flame retardant composition of this example contains 3 to 6% by weight of pentaerythritol, a composite material having excellent adhesion between the base sheet and the flame retardant composition and improved flame retardancy and sound absorption can be provided.
만약, 본 실시예의 난연 조성물이 총 중량 기준으로 펜타에리트리톨을 1 중량% 미만으로 포함할 경우에는, 상기 펜타에리트리톨을 1 ~ 8 중량%로 포함하는 경우 보다, 기재 시트 내부로의 난연 조성물의 침투성이 저하되어, 전반적인 특성이 저하될 수 있다. 반면, 본 실시예의 난연 조성물이 총 중량 기준으로 펜타에리트리톨을 8 중량% 초과로 포함할 경우에는, 상기 펜타에리트리톨을 1 ~ 8 중량%로 포함하는 경우 보다, 기재 시트와 난연 조성물 간의 접착성이 저하되어, 난연성 및 흡음성이 저하될 수 있다.If the flame retardant composition of this example contains less than 1% by weight of pentaerythritol based on the total weight, the flame retardant composition inside the base sheet is more concentrated than when it contains 1 to 8% by weight of pentaerythritol. As permeability decreases, overall properties may deteriorate. On the other hand, when the flame retardant composition of this example contains more than 8% by weight of pentaerythritol based on the total weight, the adhesiveness between the base sheet and the flame retardant composition is lower than when it contains 1 to 8% by weight of pentaerythritol. As this decreases, flame retardancy and sound absorption may decrease.
본 실시예의 난연 조성물은 인산 암모늄을 포함하되, 상기 난연 조성물 총 중량 기준으로 인산 암모늄을 15 ~ 25 중량%, 구체적으로는 16 ~ 23 중량%, 더 구체적으로는 17 ~ 20 중량%로 포함할 수 있다. 특히, 본 실시예의 난연 조성물이 인산 암모늄을 15 ~ 25 중량%로 포함할 때, 기재 시트와 난연 조성물 간의 접착성이 우수하면서도 난연성 및 흡음성이 향상된, 복합소재를 제공할 수 있다.The flame retardant composition of this embodiment includes ammonium phosphate, and may include 15 to 25% by weight, specifically 16 to 23% by weight, and more specifically 17 to 20% by weight, based on the total weight of the flame retardant composition. there is. In particular, when the flame retardant composition of this example contains 15 to 25% by weight of ammonium phosphate, a composite material having excellent adhesion between the base sheet and the flame retardant composition and improved flame retardancy and sound absorption can be provided.
만약, 본 실시예의 난연 조성물이 총 중량 기준으로 인산 암모늄을 15 중량% 미만으로 포함할 경우에는, 상기 인산 암모늄을 15 ~ 25 중량%로 포함하는 경우 보다, 난연성 및 흡음성이 저하될 수 있다. 반면, 본 실시예의 난연 조성물이 총 중량 기준으로 인산 암모늄을 25 중량 초과로 포함할 경우에는, 상기 인산 암모늄을 15 ~ 25 중량%로 포함하는 경우 보다, 기재 시트와 난연 조성물 간의 접착성이 저하되며, 난연성 및 흡음성이 저하될 수 있다.If the flame retardant composition of this example contains less than 15% by weight of ammonium phosphate based on the total weight, flame retardancy and sound absorption may be lowered than when it contains 15 to 25% by weight of ammonium phosphate. On the other hand, when the flame retardant composition of this example contains more than 25% by weight of ammonium phosphate based on the total weight, the adhesion between the base sheet and the flame retardant composition decreases compared to the case where the ammonium phosphate is included at 15 to 25% by weight. , flame retardancy and sound absorption may be reduced.
본 실시예의 난연 조성물은 붕산을 포함하되, 상기 난연 조성물 총 중량 기준으로 붕산을 7 ~ 15 중량%, 구체적으로는 8 ~ 14 중량%, 더 구체적으로는 10 ~ 13 중량%로 포함할 수 있다. 특히, 본 실시예의 난연 조성물이 붕산을 7 ~ 15 중량%로 포함할 때, 기재 시트와 난연 조성물 간의 접착성이 우수하면서도 난연성 및 흡음성이 향상된, 복합소재를 제공할 수 있다.The flame retardant composition of this embodiment includes boric acid, and may include 7 to 15% by weight, specifically 8 to 14% by weight, and more specifically 10 to 13% by weight, based on the total weight of the flame retardant composition. In particular, when the flame retardant composition of this example contains 7 to 15% by weight of boric acid, a composite material with excellent adhesion between the base sheet and the flame retardant composition and improved flame retardancy and sound absorption can be provided.
만약, 본 실시예의 난연 조성물이 총 중량 기준으로 붕산을 7 중량% 미만으로 포함할 경우에는, 상기 붕산을 7 ~ 15 중량%로 포함하는 경우 보다, 난연성이 저하될 수 있다. 반면, 본 실시예의 난연 조성물이 총 중량 기준으로 붕산을 15 중량% 초과로 포함할 경우에는, 상기 붕산을 7 ~ 15 중량%로 포함하는 경우 보다, 기재 시트와 난연 조성물 간의 접착성이 저하되며, 난연성 및 흡음성이 저하될 수 있다.If the flame retardant composition of this example contains less than 7% by weight of boric acid based on the total weight, the flame retardancy may be lowered than when it contains 7 to 15% by weight of boric acid. On the other hand, when the flame retardant composition of this example contains more than 15% by weight of boric acid based on the total weight, the adhesion between the base sheet and the flame retardant composition decreases compared to the case where it contains 7 to 15% by weight of boric acid, Flame retardancy and sound absorption may be reduced.
본 실시예의 난연 조성물은 바인더를 포함하며, 상기 바인더는 비닐아세테이트-에틸렌 공중합체(Ethylene Vinyl Acetate) 및 수용성 스티렌 부타디엔 고무(Styrene Butadiene Rubber)로 이루어진 군에서 선택되는 하나 이상을 포함할 수 있다.The flame retardant composition of this embodiment includes a binder, and the binder may include one or more selected from the group consisting of vinyl acetate-ethylene copolymer (Ethylene Vinyl Acetate) and water-soluble styrene butadiene rubber.
구체적으로, 본 실시예의 바인더는 비닐아세테이트-에틸렌 공중합체(Ethylene Vinyl Acetate) 및 수용성 스티렌 부타디엔 고무(Styrene Butadiene Rubber)를 모두 포함할 수 있으며, 이 경우 기재 시트와 난연 조성물 간의 부착성은 더욱 향상되어, 전반적인 난연성 및 흡음성이 더욱 향상될 수 있다.Specifically, the binder of this embodiment may include both vinyl acetate-ethylene copolymer (Ethylene Vinyl Acetate) and water-soluble styrene butadiene rubber. In this case, the adhesion between the base sheet and the flame retardant composition is further improved, The overall flame retardancy and sound absorption can be further improved.
더 구체적으로, 본 실시예의 바인더는 비닐아세테이트-에틸렌 공중합체(Ethylene Vinyl Acetate) 및 수용성 스티렌 부타디엔 고무(Styrene Butadiene Rubber)를 1 : 5 ~ 15 의 중량비로 포함할 수 있으며, 두 성분이 상기 중량비로 포함될 때, 기재 시트와 난연 조성물 간의 부착성이 우수하면서도 전반적인 난연성 및 흡음성이 우수한 복합소재를 제공할 수 있다.More specifically, the binder of this embodiment may include vinyl acetate-ethylene copolymer (Ethylene Vinyl Acetate) and water-soluble styrene butadiene rubber in a weight ratio of 1:5 to 15, and the two components are mixed in the above weight ratio. When included, it is possible to provide a composite material with excellent adhesion between the base sheet and the flame retardant composition and excellent overall flame retardancy and sound absorption.
가장 구체적으로, 본 실시예의 바인더는 비닐아세테이트-에틸렌 공중합체(Ethylene Vinyl Acetate) 및 수용성 스티렌 부타디엔 고무(Styrene Butadiene Rubber)를 1 : 10 ~ 12 의 중량비로 포함할 수 있으며, 두 성분이 상기 중량비로 포함될 때, 기재 시트와 난연 조성물 간의 부착성이 현저히 우수하면서도 전반적인 난연성 및 흡음성이 현저히 우수한 복합소재를 제공할 수 있다.Most specifically, the binder of this embodiment may include vinyl acetate-ethylene copolymer (Ethylene Vinyl Acetate) and water-soluble styrene butadiene rubber in a weight ratio of 1:10 to 12, and the two components are mixed in the above weight ratio. When included, it is possible to provide a composite material that has significantly excellent adhesion between the base sheet and the flame retardant composition while also having significantly excellent overall flame retardancy and sound absorption.
이때, 본 실시예의 비닐아세테이트-에틸렌 공중합체는 중량평균 분자량(Mw)이 10,000 ~ 50,000 g/mol, 구체적으로는 15,000 ~ 30,000 g/mol, 더 구체적으로는 20,000 ~ 30,000 g/mol 일 수 있다. 특히, 본 실시예의 비닐아세테이트-에틸렌 공중합체의 중량평균 분자량이 20,000 ~ 30,000 g/mol 일 때, 부착성이 현저히 우수하여, 난연성 및 이의 지속성과 흡음성이 우수할 수 있다.At this time, the vinyl acetate-ethylene copolymer of this example may have a weight average molecular weight (Mw) of 10,000 to 50,000 g/mol, specifically 15,000 to 30,000 g/mol, and more specifically 20,000 to 30,000 g/mol. In particular, when the weight average molecular weight of the vinyl acetate-ethylene copolymer of this example is 20,000 to 30,000 g/mol, adhesion is significantly excellent, and flame retardancy, sustainability, and sound absorption can be excellent.
만약, 상기 비닐아세테이트-에틸렌 공중합체의 중량 평균 분자량이 10,000 g/mol 미만이거나, 50,000 g/mol 초과인 경우에는, 이외 성분들과의 상용성이 좋지 못하거나, 셀룰로오스 섬유 조직 내부로 균일하게 침투되지 못하여, 기재 시트와 난연 조성물 간의 부착성이 저하되고, 전반적인 난연성 및 흡음성이 저하될 수 있다.If the weight average molecular weight of the vinyl acetate-ethylene copolymer is less than 10,000 g/mol or more than 50,000 g/mol, compatibility with other components is poor or it does not uniformly penetrate into the cellulose fiber tissue. If this is not possible, the adhesion between the base sheet and the flame retardant composition may be reduced, and the overall flame retardancy and sound absorption may be reduced.
본 실시예의 난연 조성물은 상기 바인더를 포함하되, 상기 난연 조성물 총 중량 기준으로 3 ~ 8 중량%, 구체적으로는 5 ~ 7 중량%로 포함할 수 있다. 특히, 본 실시예의 난연 조성물이 바인더를 3 ~ 8 중량%로 포함할 때, 기재 시트와 난연 조성물 간의 접착성이 우수하면서도 난연성 및 흡음성이 향상된, 복합소재를 제공할 수 있다. The flame retardant composition of this embodiment includes the binder, and may include 3 to 8 wt%, specifically 5 to 7 wt%, based on the total weight of the flame retardant composition. In particular, when the flame retardant composition of this example includes 3 to 8% by weight of the binder, a composite material with excellent adhesion between the base sheet and the flame retardant composition and improved flame retardancy and sound absorption can be provided.
만약, 본 실시예의 난연 조성물이 총 중량 기준으로 바인더를 3 중량% 미만으로 포함할 경우에는, 상기 바인더를 3 ~ 8 중량%로 포함하는 경우 보다, 기재 시트와 난연 조성물 간의 부착성이 현저히 저하될 수 있다. 반면, 본 실시예의 난연 조성물이 총 중량 기준으로 바인더를 8 중량% 초과로 포함할 경우에는, 셀룰로오스 섬유 내부 조직으로 난연 조성물이 쉽게 침투하기 어렵고, 기재 시트 표면에 단순 엉김 현상을 나타내는 문제가 있어, 기재 시트와 난연 조성물 간의 접착성, 난연성 및 흡음성이 현저히 저하될 수 있다.If the flame retardant composition of this example contains less than 3% by weight of the binder based on the total weight, the adhesion between the base sheet and the flame retardant composition will be significantly reduced compared to the case where the binder is included at 3 to 8% by weight. You can. On the other hand, when the flame retardant composition of this example contains more than 8% by weight of binder based on the total weight, it is difficult for the flame retardant composition to easily penetrate into the internal tissue of the cellulose fibers, and there is a problem of simple agglomeration on the surface of the base sheet, Adhesion, flame retardancy, and sound absorption between the base sheet and the flame retardant composition may be significantly reduced.
본 실시예의 난연 조성물은 상기된 성분과 함께, 잔량의 물을 포함할 수 있다. 또한, 본 실시예의 난연 조성물은 분산제, 계면활성제, 안료, 소포제, 산화 방지제, 변색 방지제, 가소제 및 용매로 이루어진 군에서 선택되는 하나 이상을 더 포함할 수 있으나, 이에 제한되지 않는다.The flame retardant composition of this embodiment may include the above-mentioned components along with a residual amount of water. Additionally, the flame retardant composition of this embodiment may further include one or more selected from the group consisting of dispersants, surfactants, pigments, anti-foaming agents, antioxidants, discoloration inhibitors, plasticizers, and solvents, but is not limited thereto.
상기된 셀룰로오스 섬유로 형성된 기재 시트; 및 상기 기재 시트에 함침된 셀룰로오스 섬유용 난연 조성물을 포함하는 복합소재는, 건축재, 자동차 내장재, 포장재 및/또는 기계 단열재일 수 있으나, 이에 제한되지 않는다. 예를 들어, 상기 건축재는 실내 벽 또는 천장 등에 설치되는 실내 마감재일 수 있으나, 이에 제한되지 않는다.A base sheet formed from the cellulose fibers described above; And the composite material containing the flame retardant composition for cellulose fibers impregnated in the base sheet may be, but is not limited to, building materials, automobile interior materials, packaging materials, and/or mechanical insulation materials. For example, the building material may be an interior finishing material installed on an indoor wall or ceiling, but is not limited thereto.
이하 실시예, 비교예, 및 실험예를 통하여 본 발명의 난연성 및 흡음성이 향상된 셀룰로오스 섬유 기반의 친환경 복합소재에 대해 구체적으로 설명하기로 한다. 이들 실시예는 단지 본 발명을 예시하기 위한 것이므로, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지는 않는다.Hereinafter, the eco-friendly composite material based on cellulose fiber with improved flame retardancy and sound absorption of the present invention will be described in detail through Examples, Comparative Examples, and Experimental Examples. Since these examples are merely for illustrating the present invention, the scope of the present invention is not to be construed as limited by these examples.
[ 실시예 ][Example]
실시예 1 내지 5Examples 1 to 5
표 1[단위 : 중량%]에 따라 난연 조성물을 제조하되, 표 1에서 바인더는 표 2[단위 : 중량비]에 따라, 비닐아세테이트-에틸렌 공중합체 및 수용성 스티렌 부타디엔 고무가 혼합된 것을 사용하였다.A flame retardant composition was prepared according to Table 1 [unit: weight %], and the binder in Table 1 was a mixture of vinyl acetate-ethylene copolymer and water-soluble styrene butadiene rubber according to Table 2 [unit: weight ratio].
구체적으로, 40 ~ 42 ℃의 물에 황산 암모늄을 투입 및 교반하고, 혼합물의 온도를 47 ~ 49 ℃로 가온한 뒤, 디시안디아마이드를 투입 및 교반하였다. 이어서, 혼합물의 온도를 52 ~ 54 ℃로 가온한 뒤, 펜타에리트리톨을 투입 및 교반하고, 혼합물의 온도를 59 ~ 61 ℃로 가온한 뒤, 인산 암모늄을 투입 및 교반하고, 마지막으로 혼합물의 온도를 74 ~ 76 ℃로 가온한 뒤, 붕산 및 바인더를 투입 및 교반함으로써, 난연 조성물을 제조하였다.Specifically, ammonium sulfate was added to and stirred in water at 40 to 42°C, the temperature of the mixture was heated to 47 to 49°C, and then dicyandiamide was added and stirred. Next, the temperature of the mixture was warmed to 52 ~ 54 ℃, pentaerythritol was added and stirred, the temperature of the mixture was warmed to 59 ~ 61 ℃, ammonium phosphate was added and stirred, and finally, the temperature of the mixture was adjusted to 59 ~ 61 ℃. After heating to 74-76°C, boric acid and binder were added and stirred to prepare a flame retardant composition.
상기에 따라 제조된 난연 조성물을, 셀룰로오스 섬유로 형성된 부직포 형태의 기재 시트(두께 : 3.5 mm)에 함침 및 경화시킴으로써, 실내 마감재로 활용 가능한 복합소재(시료 중량 : 180 g/m2)를 제조하였다. A composite material (sample weight: 180 g/m 2 ) that can be used as an interior finishing material was prepared by impregnating and curing the flame retardant composition prepared as above into a non-woven fabric-type base sheet (thickness: 3.5 mm) made of cellulose fibers. .
이때, 표 2에서 비닐아세테이트-에틸렌 공중합체는, 중량평균 분자량이 20,000 ~ 30,000 g/mol 인 것을 사용하였다.At this time, the vinyl acetate-ethylene copolymer in Table 2 was used having a weight average molecular weight of 20,000 to 30,000 g/mol.
[ 비교예 ] [Comparative example]
비교예 1 내지 12Comparative Examples 1 to 12
표 3[단위 : 중량%] 및 표 4[단위 : 중량%]에 따라 난연 조성물을 제조한 것을 제외하고는, 실시예 3과 동일하게 실시하였다.The same procedure as Example 3 was carried out, except that the flame retardant composition was prepared according to Table 3 [unit: weight %] and Table 4 [unit: weight %].
비교예 13Comparative Example 13
바인더로 비닐아세테이트-에틸렌 공중합체만 포함(수용성 스티렌 부타디엔 고무 포함 X)하는 것을 제외하고는, 실시예 3과 동일하게 실시하였다.The same procedure as Example 3 was carried out, except that only vinyl acetate-ethylene copolymer was included as a binder (X including water-soluble styrene butadiene rubber).
비교예 14Comparative Example 14
바인더로 수용성 스티렌 부타디엔 고무만 포함하는 것을 제외하고는, 실시예 3과 동일하게 실시하였다.The same procedure as Example 3 was carried out, except that only water-soluble styrene butadiene rubber was included as a binder.
비교예 15Comparative Example 15
중량평균 분자량이 100,000 ~ 150,000 g/mol 인 비닐아세테이트-에틸렌 공중합체를 사용한 것을 제외하고는, 실시예 3과 동일하게 실시하였다.The same procedure as Example 3 was performed, except that a vinyl acetate-ethylene copolymer with a weight average molecular weight of 100,000 to 150,000 g/mol was used.
[ 실험예 ] [Experimental example]
실험예 1 : 접착성 평가Experimental Example 1: Adhesion evaluation
상기 실시예 및 비교예의 제조에 사용된 난연 조성물만 별도로 취하여, 이의 접착성을 평가하였다.Only the flame retardant compositions used in the preparation of the above examples and comparative examples were taken separately and their adhesiveness was evaluated.
구체적으로, Cross-cut 시험법(ASTM D 3359 시험규격)에 따라, 실시예 및 비교예에 따르는 난연 조성물의 부착성을 하기 기준에 따라 평가하고, 그 결과를 표 5에 나타내었다.Specifically, according to the cross-cut test method (ASTM D 3359 test standard), the adhesion of the flame retardant compositions according to Examples and Comparative Examples was evaluated according to the following criteria, and the results are shown in Table 5.
이때, 표 5에는 5회 실험을 반복한 평균값을 기재하였으며, 5B 일 경우에 부착성이 가장 우수함을 의미한다.At this time, Table 5 shows the average value of five repeated experiments, which means that 5B has the best adhesion.
0B : 분리된 면적이 65 % 이상0B: Separated area is more than 65%
1B : 분리된 면적이 35 ~ 65 %1B: Separated area is 35 to 65%
2B : 분리된 면적이 15 ~ 35 %2B: Separated area is 15 to 35%
3B : 분리된 면적이 5 ~ 15 % 3B: Separated area is 5 to 15%
4B : 분리된 면적이 5 % 이하4B: Separated area is less than 5%
5B : 분리된 면적이 0 %5B: Separated area is 0%
표 5를 보면, 본 실시예에 따를 경우, 난연 조성물의 접착성이 현저히 우수함을 알 수 있다.Looking at Table 5, it can be seen that according to this example, the adhesiveness of the flame retardant composition is significantly excellent.
실험예 2 : 난연성 평가Experimental Example 2: Flame retardancy evaluation
(1) 난연성 평가 1(1) Flame retardancy evaluation 1
실시예 및 비교예에 따르는 복합소재의 난연성을 KS F 2805:2004 시험법에 따라 측정하였다.The flame retardancy of the composite materials according to Examples and Comparative Examples was measured according to the KS F 2805:2004 test method.
이때, 표 6에는 복합소재를 제조한 후 별도의 처리를 하지 않은 상태에서 측정한 난연성(A)과, 복합소재를 약 100 회 정도 구기고 피는 과정을 반복한 다음에 측정한 난연성(B)을 기재하였다. At this time, Table 6 lists the flame retardancy (A) measured without any additional treatment after manufacturing the composite material, and the flame retardancy (B) measured after repeating the process of crumpling and bending the composite material about 100 times. did.
표 6을 보면, 본 실시예에 따를 경우, 난연성은 모두 2 등급 이상으로, 준불연 수준을 구현함을 알 수 있다.Looking at Table 6, it can be seen that according to this embodiment, the flame retardancy is all grade 2 or higher, realizing a semi-non-flammable level.
또한, 본 실시예에 따를 경우, 복합소재를 구부렸다 피는 조작을 여러회 반복하여도 난연성이 저하되지 않고 유지되는 바, 본 실시예에 따르는 난연 조성물은 셀룰로오스 섬유로 형성된 기재 시트와의 접착성이 우수함을 알 수 있다.In addition, according to this example, the flame retardancy is maintained without deterioration even after bending and bending the composite material several times, and the flame retardant composition according to this example has excellent adhesion to the base sheet formed of cellulose fibers. can be seen.
(2) 난연성 평가 2(2) Flame retardancy evaluation 2
실시예 및 비교예의 복합소재를 상온 조건에서, 포켓용 제트분사토치(GF-863)을 이용하여, 약 800 ℃에서 120 초 동안 노출시킨 뒤, 육안으로의 변화를 관찰하여, 그 결과를 도 1 내지 4에 나타내었다.The composite materials of Examples and Comparative Examples were exposed to about 800° C. for 120 seconds under room temperature conditions using a pocket jet jet torch (GF-863), and changes were observed with the naked eye. The results are shown in Figure 1. Shown in to 4.
이때, 도 1 내지 4는 표 7의 결과를 나타낸다.At this time, Figures 1 to 4 show the results in Table 7.
도 1을 보면, 본 실시예에 따를 경우, 불에 노출되어 그을림은 발생되나, 불에 타 구멍이 발생되는 현상은 보이지 않았다. 반면, 본 실시예에 따르지 않는 비교예 1, 9 및 12의 경우에는, 그을림이 발생됨과 동시에 불에타 구멍이 발생되는 현상이 확인되었다.Looking at FIG. 1, according to this embodiment, charring occurred due to exposure to fire, but no hole was created by burning. On the other hand, in the case of Comparative Examples 1, 9, and 12, which did not follow this example, it was confirmed that charring occurred and at the same time, burning holes were created.
즉, 본 실시예에 따를 경우, 난연 성능이 더욱 우수함을 알 수 있다.That is, it can be seen that according to this embodiment, flame retardant performance is more excellent.
실험예 3 : 흡음성 평가Experimental Example 3: Sound absorption evaluation
실시예 및 비교예의 복합소재의 흡음계수를 KS F 2805:2014 에 따라 평가하고, 5 회 반복한 결과의 평균치를 표 8[단위 : 초]에 나타내었다. 이때, 표 8에는 5회 반복한 결과의 평균치를 기재하되, 소수점 이하 둘째 자리까지만 표기되도록 하였다.The sound absorption coefficient of the composite materials of Examples and Comparative Examples was evaluated according to KS F 2805:2014, and the average value of the results repeated 5 times is shown in Table 8 [unit: seconds]. At this time, Table 8 lists the average value of the results repeated five times, but only to two decimal places.
표 8을 보면, 본 실시예에 따를 경우, 흡음성이 우수함을 알 수 있다.Looking at Table 8, it can be seen that according to this example, sound absorption is excellent.
전술한 바와 같이, 본 발명의 설명은 예시를 위한 것이며, 본 발명이 속하는 기술분야의 통상의 기술을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다. 그러므로, 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며, 한정적이 아닌 것으로 이해해야만 한다. 예를 들어, 단일형으로 설명되어 있는 각 구성 요소는 분산되어 실시될 수도 있으며, 마찬가지로 분산된 것으로 설명되어 있는 구성 요소들도 결합된 형태로 실시될 수 있다.As described above, the description of the present invention is for illustrative purposes, and a person skilled in the art to which the present invention pertains can easily transform it into another specific form without changing the technical idea or essential features of the present invention. You will understand. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. For example, each component described as single may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form.
본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present invention. do.
Claims (5)
상기 기재 시트에 함침된 셀룰로오스 섬유용 난연 조성물;을 포함하되,
상기 셀룰로오스 섬유용 난연 조성물은
상기 셀룰로오스 섬유용 난연 조성물 총 중량 기준으로 황산 암모늄 10 ~ 20 중량%, 디시안디아마이드(Dicyandiamide) 7 ~ 13 중량%, 펜타에리트리톨 1 ~ 8 중량%, 인산 암모늄 15 ~ 25 중량%, 붕산 7 ~ 15 중량% 및 바인더 3 ~ 8 중량%를 포함하며,
상기 바인더는
비닐아세테이트-에틸렌 공중합체(Ethylene Vinyl Acetate) 및 수용성 스티렌 부타디엔 고무(Styrene Butadiene Rubber)를 1 : 5 ~ 15 의 중량비로 포함하는 것을 특징으로 하는, 난연성이 우수한 셀룰로오스 섬유 기반의 흡음용 친환경 복합소재.
A base sheet formed of cellulose fibers; and
A flame retardant composition for cellulose fibers impregnated in the base sheet,
The flame retardant composition for cellulose fiber is
Based on the total weight of the flame retardant composition for cellulose fiber, 10 to 20% by weight of ammonium sulfate, 7 to 13% by weight of dicyandiamide, 1 to 8% by weight of pentaerythritol, 15 to 25% by weight of ammonium phosphate, and 7 to 7% by weight of boric acid. 15% by weight and 3 to 8% by weight binder,
The binder is
An eco-friendly sound-absorbing composite material based on cellulose fibers with excellent flame retardancy, characterized in that it contains vinyl acetate-ethylene copolymer (Ethylene Vinyl Acetate) and water-soluble styrene butadiene rubber in a weight ratio of 1:5 to 15.
상기 난연 조성물은
분산제, 계면활성제, 안료, 소포제, 산화 방지제, 변색 방지제, 가소제 및 용매로 이루어진 군에서 선택되는 하나 이상을 더 포함하는 것을 특징으로 하는, 난연성이 우수한 셀룰로오스 섬유 기반의 흡음용 친환경 복합소재.
According to claim 1,
The flame retardant composition is
An eco-friendly sound-absorbing composite material based on cellulose fibers with excellent flame retardancy, characterized in that it further comprises at least one selected from the group consisting of dispersants, surfactants, pigments, anti-foaming agents, antioxidants, discoloration inhibitors, plasticizers and solvents.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006110965A (en) * | 2004-10-13 | 2006-04-27 | Toshihiro Nakahara | Fire retardancy imparting liquid material for wood, and its manufacturing method |
| JP2006214063A (en) * | 2005-02-07 | 2006-08-17 | Toray International Inc | Nonflammable fiber product |
| JP2013136852A (en) * | 2011-12-28 | 2013-07-11 | Raizu Chemical Research:Kk | Flame-retardant composition for fiber coating processing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102278958B1 (en) | 2017-03-24 | 2021-07-19 | 엘지전자 주식회사 | Method of preparing nanocellulose and silica aerogel composite material comprising nanocellulose |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006110965A (en) * | 2004-10-13 | 2006-04-27 | Toshihiro Nakahara | Fire retardancy imparting liquid material for wood, and its manufacturing method |
| JP2006214063A (en) * | 2005-02-07 | 2006-08-17 | Toray International Inc | Nonflammable fiber product |
| JP2013136852A (en) * | 2011-12-28 | 2013-07-11 | Raizu Chemical Research:Kk | Flame-retardant composition for fiber coating processing |
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| KR20230055505A (en) | 2023-04-26 |
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