JPH04342764A - Foamable fire-resisting material - Google Patents
Foamable fire-resisting materialInfo
- Publication number
- JPH04342764A JPH04342764A JP11594391A JP11594391A JPH04342764A JP H04342764 A JPH04342764 A JP H04342764A JP 11594391 A JP11594391 A JP 11594391A JP 11594391 A JP11594391 A JP 11594391A JP H04342764 A JPH04342764 A JP H04342764A
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- resin
- fire
- resin composite
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000010439 graphite Substances 0.000 claims abstract description 96
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 96
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 239000000805 composite resin Substances 0.000 claims abstract description 21
- 239000005011 phenolic resin Substances 0.000 claims description 34
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 32
- 238000009830 intercalation Methods 0.000 claims description 29
- 230000002687 intercalation Effects 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 26
- 239000002131 composite material Substances 0.000 claims description 19
- 229920000877 Melamine resin Polymers 0.000 claims description 17
- 235000019256 formaldehyde Nutrition 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 150000002989 phenols Chemical class 0.000 claims description 13
- 239000007849 furan resin Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000004640 Melamine resin Substances 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011819 refractory material Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 150000007974 melamines Chemical class 0.000 claims description 3
- 239000000779 smoke Substances 0.000 abstract description 9
- 230000009970 fire resistant effect Effects 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 5
- -1 graphite compound Chemical class 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000002245 particle Substances 0.000 description 20
- 229920001568 phenolic resin Polymers 0.000 description 17
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical group OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 9
- 230000005611 electricity Effects 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007809 chemical reaction catalyst Substances 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- 239000004312 hexamethylene tetramine Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical group O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- PCNMALATRPXTKX-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(C)(O)C=C1 PCNMALATRPXTKX-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-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
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PVAONLSZTBKFKM-UHFFFAOYSA-N diphenylmethanediol Chemical compound C=1C=CC=CC=1C(O)(O)C1=CC=CC=C1 PVAONLSZTBKFKM-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、防火扉、防火壁などに
耐火性を与えるために使用される発泡性耐火材料に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foamable fireproof material used to provide fire resistance to fire doors, fire walls, etc.
【０００２】0002
【従来の技術】火災時における防火扉や防火壁などの役
割は火炎や煙等の進行を遮断して、火災が拡大すること
を阻止すると共に煙や有毒ガスの拡散を阻止し、建物内
からの安全な非難を確保しようとするものである。この
ために防火扉や防火壁には火炎による高温の作用に耐え
る耐火層が形成されており、この耐火層を形成する材料
としては各種のものが提供されている。例えば珪酸カル
シウムや石膏、木毛セメントなど無機質水硬性物質をバ
インダーとする材料や、珪酸ソーダなどガラス状物質を
バインダーとする材料等が従来から使用されている。[Prior Art] The role of fire doors and fire walls in the event of a fire is to block the progress of flames and smoke, prevent the fire from spreading, and prevent the spread of smoke and toxic gases from inside the building. It seeks to ensure safe condemnation. For this reason, fireproof doors and fireproof walls are provided with a fireproof layer that can withstand the effects of high temperatures caused by flames, and various materials are available for forming this fireproof layer. For example, materials that use as a binder an inorganic hydraulic substance such as calcium silicate, gypsum, or wood wool cement, or materials that use a glassy substance such as sodium silicate as a binder have been used conventionally.
【０００３】0003
【発明が解決しようとする課題】しかしこれらの材料で
形成される耐火層では、局所的に火炎が作用して局所的
に高温が作用すると、この高温が局所的に作用する部分
において耐火層に亀裂等が発生して、この亀裂から火炎
が侵入したり煙が侵入したりするおそれがあり、火災の
拡大や煙等の拡散を阻止することが十分におこなうこと
ができないという問題があった。[Problems to be Solved by the Invention] However, in the fireproof layer formed of these materials, when flame acts locally and high temperature acts locally, the fireproof layer is damaged in the area where the high temperature locally acts. There is a risk that cracks may occur and flame or smoke may enter through the cracks, and there is a problem in that it is not possible to sufficiently prevent the spread of fire or the spread of smoke.
【０００４】また近年の高度な情報化社会の発展に伴っ
てオフィスビルでは各種の電子機器が建築物内に設置さ
れるようになっており、このような電子機器は電磁波の
作用や静電気の作用で誤動作するおそれがあり、電子機
器を設置する室内においては電磁波障害や静電気障害に
対処する必要がある。しかし上記のような材料で形成さ
れる耐火層では、電磁波をシールドすることができず、
また静電気をアースすることができず、電磁波障害や静
電気障害に対処することは不可能である。[0004] Furthermore, with the development of an advanced information society in recent years, various electronic devices are being installed in office buildings, and such electronic devices are susceptible to the effects of electromagnetic waves and static electricity. Therefore, it is necessary to take precautions against electromagnetic interference and static electricity interference in rooms where electronic equipment is installed. However, the fireproof layer made of the above materials cannot shield electromagnetic waves.
Furthermore, static electricity cannot be grounded, and it is impossible to deal with electromagnetic interference or static electricity interference.
【０００５】本発明は上記の点に鑑みてなされたもので
あり、火災の拡大や煙等の拡散を確実に阻止することが
できると共に電磁波障害や静電気障害に対処することも
でき、加えてシート状等に容易に成形して耐火層を形成
することができる発泡性耐火材料を提供することを目的
とするものである。The present invention has been made in view of the above points, and can reliably prevent the spread of fire and the spread of smoke, etc., and can also deal with electromagnetic interference and static electricity interference. The object of the present invention is to provide a foamable fireproof material that can be easily formed into a shape to form a fireproof layer.
【０００６】[0006]
【課題を解決するための手段】本発明に係る発泡性耐火
材料は、樹脂と黒鉛類粉末とを混合して調製される黒鉛
・樹脂複合材と、黒鉛層間化合物とを配合して成ること
を特徴とするものである。また本発明に係る他の発泡性
耐火材料は、樹脂原料を黒鉛類粉末と混合させつつ反応
させて調製される黒鉛・樹脂複合材と、黒鉛層間化合物
とを配合して成ることを特徴とするものである。[Means for Solving the Problems] The foamable fireproof material according to the present invention is composed of a graphite-resin composite prepared by mixing a resin and graphite powder, and a graphite intercalation compound. This is a characteristic feature. Another foamable fireproof material according to the present invention is characterized in that it is made by blending a graphite-resin composite material prepared by mixing and reacting a resin raw material with graphite powder, and a graphite intercalation compound. It is something.
【０００７】本発明において、黒鉛層間化合物としては
黒鉛の層状結晶の層間に硫酸が挿入されたものが使用さ
れる。また本発明において樹脂としてはフェノール樹脂
やメラミン樹脂、フラン樹脂が使用される。以下、本発
明を詳細に説明する。まず、樹脂と黒鉛類粉末とを混合
して調製される黒鉛・樹脂複合材と、黒鉛層間化合物と
を配合して得られる発泡性耐火材料について説明する。
樹脂としては特に限定されるものではなく、熱硬化性樹
脂一般を使用することができるが、中でもフェノール樹
脂やメラミン樹脂、フラン樹脂を使用するのが好ましい
。また本発明において黒鉛類の粉末としては炭素質の粉
末であれば一般に使用することができるものであり、例
えば天然黒鉛、人造黒鉛、カーボンブラック、コークス
粉末、木炭粉末などを用いることができ、これらを一種
単独であるいは複数種混合して使用することができる。
黒鉛類粉末の粒径は特に限定されるものではないが、平
均粒径が１００μｍ 以下であるものが好ましい。
そして上記樹脂と黒鉛類粉末とをニーダーその他の混合
装置を用い混合・混練することによって黒鉛・樹脂複合
材を調製することができる。次にこの黒鉛・樹脂複合材
に黒鉛層間化合物を配合して混合することによって、本
発明に係る発泡性耐火材を得ることができる。黒鉛は炭
素の六角網状平面が積み重なった結晶構造をしており、
この網状平面の層間に各種の物質を挿入させることによ
って黒鉛層間化合物を得ることができる。この黒鉛層間
化合物は、天然黒鉛や人造黒鉛などの粉末に例えば濃硫
酸と酸化剤との混酸を添加攪拌して、黒鉛の層状結晶の
層間に硫酸を挿入させることによって調製することがで
きる。この酸化剤としては硝酸など各種のものを使用す
ることができる。このように調製される黒鉛層間化合物
は層間に硫酸が挿入されているために、３００℃以上の
高温で加熱とすると層間の硫酸が分解してガス化し、そ
の圧力で黒鉛層間が層面と垂直な方向に離れて大きく膨
張する性質を有するものであり、黒鉛層間化合物は膨脹
化黒鉛とも称されるものである。黒鉛層間化合物の配合
量は耐火層の所望する発泡倍率（膨脹倍率）に応じて任
意に設定されるものであるが、一般的には黒鉛・樹脂複
合材１００重量部に対して１〜３０重量部の範囲が好ま
しい。In the present invention, the graphite intercalation compound used is one in which sulfuric acid is inserted between the layers of graphite layered crystals. Further, in the present invention, phenol resin, melamine resin, and furan resin are used as the resin. The present invention will be explained in detail below. First, a foamable fireproof material obtained by blending a graphite/resin composite material prepared by mixing a resin and a graphite powder with a graphite intercalation compound will be described. The resin is not particularly limited, and general thermosetting resins can be used, but among them, phenol resins, melamine resins, and furan resins are preferably used. Further, in the present invention, as the graphite powder, any carbonaceous powder can be generally used.For example, natural graphite, artificial graphite, carbon black, coke powder, charcoal powder, etc. can be used. These can be used singly or in combination. Although the particle size of the graphite powder is not particularly limited, it is preferable that the average particle size is 100 μm or less. A graphite/resin composite material can be prepared by mixing and kneading the resin and graphite powder using a kneader or other mixing device. Next, by blending and mixing a graphite intercalation compound with this graphite/resin composite material, the foamable fireproof material according to the present invention can be obtained. Graphite has a crystal structure in which hexagonal network planes of carbon are piled up.
A graphite intercalation compound can be obtained by inserting various substances between the layers of this net-like plane. This graphite intercalation compound can be prepared by adding and stirring, for example, a mixed acid of concentrated sulfuric acid and an oxidizing agent to a powder of natural graphite or artificial graphite, and thereby inserting sulfuric acid between the layers of layered graphite crystals. Various oxidizing agents such as nitric acid can be used as the oxidizing agent. Since the graphite intercalation compound prepared in this way has sulfuric acid inserted between the layers, when heated at a high temperature of 300°C or higher, the sulfuric acid between the layers decomposes and gasifies, and the pressure causes the graphite interlayers to become perpendicular to the layer plane. The graphite intercalation compound is also called expanded graphite because it has the property of expanding greatly in different directions. The blending amount of the graphite intercalation compound is arbitrarily set depending on the desired expansion ratio (expansion ratio) of the fireproof layer, but generally it is 1 to 30 parts by weight per 100 parts by weight of the graphite/resin composite material. A range of 50% is preferred.
【０００８】次に、樹脂原料を黒鉛類粉末と混合させつ
つ反応させて調製される黒鉛・樹脂複合材と、黒鉛層間
化合物とを配合して得られる発泡性耐火材料について説
明する。このものでは、樹脂原料を黒鉛類粉末と混合さ
せつつ反応させて調製される黒鉛・樹脂複合材において
、樹脂としてはフェノール樹脂やメラミン樹脂、フラン
樹脂が使用されるものであり、まず樹脂としてフェノー
ル樹脂を用いる場合を説明する。フェノール樹脂の場合
は樹脂原料としてフェノール類とホルムアルデヒド類と
を用い、このフェノール類とホルムアルデヒド類を触媒
の存在下で黒鉛類粉末と混合させつつ反応させることに
よって、黒鉛・樹脂複合材としての黒鉛・フェノール樹
脂粒状物を調製することができる。ここでフェノール類
とはフェノール及びフェノールの誘導体を意味するもの
であり、例えばフェノールの他にｍ‐クレゾール、レゾ
ルシノール、３， ５‐キシレノールなどの３官能性の
もの、ビスフェノールＡ、ジヒドロキシジフェニルメタ
ンなどの４官能性のもの、ｏ‐クレゾール、ｐ‐クレゾ
ール、ｐ‐ｔｅｒブチルフェノール、ｐ‐フェニルフェ
ノール、ｐ‐クミルフェノール、ｐ‐ノニルフェノール
、２， ４又は２， ６‐キシレノールなどの２官能性
のｏ‐又はｐ‐置換のフェノール類などを挙げることが
でき、さらに塩素または臭素で置換されたハロゲン化フ
ェノールなども使用することができる。もちろんこれら
から一種類選択して用いる他、複数種のものを混合して
用いることもできる。またホルムアルデヒド類としては
水溶液の形態であるホルマリンが最適であるが、パラホ
ルムアルデヒドのような形態のものを用いることもでき
、その他ホルムアルデヒドの一部あるいは大部分をフル
フラールやフルフリルアルコールに置き換えて用いるこ
とも可能である。さらに反応触媒としては、フェノール
類のベンゼン核とベンゼン核との間に−ＮＣＨ２ 結合
を生成するような塩基性物質、例えばヘキサメチレンテ
トラミン、アンモニア及びメチルアミン、ジメチルアミ
ン、エチレンジアミン、モノエタノールアミン等の第１
級や第２級のアミン類などを用いることができる。さら
にこれらと併用して、アルカリ金属やアルカリ土類金属
の水酸化物や第３級アミンなどのフェノール樹脂の合成
時に一般によく使用される塩基性触媒を用いることもで
きる。Next, a foamable fireproof material obtained by blending a graphite/resin composite material prepared by mixing and reacting a resin raw material with graphite powder and a graphite intercalation compound will be described. In this graphite/resin composite material, which is prepared by mixing resin raw materials with graphite powder and reacting them, phenol resin, melamine resin, or furan resin is used as the resin. The case where resin is used will be explained. In the case of phenolic resin, phenols and formaldehydes are used as resin raw materials, and by reacting the phenols and formaldehydes while mixing them with graphite powder in the presence of a catalyst, graphite/resin composite material is produced. Phenolic resin granules can be prepared. Phenols here mean phenol and phenol derivatives, and include, in addition to phenol, trifunctional ones such as m-cresol, resorcinol, and 3,5-xylenol, and four-functional ones such as bisphenol A and dihydroxydiphenylmethane. difunctional ones such as o-cresol, p-cresol, p-terbutylphenol, p-phenylphenol, p-cumylphenol, p-nonylphenol, 2,4 or 2,6-xylenol; Alternatively, p-substituted phenols can be used, and halogenated phenols substituted with chlorine or bromine can also be used. Of course, in addition to selecting and using one type from these, it is also possible to use a mixture of multiple types. Further, as formaldehyde, formalin in the form of an aqueous solution is most suitable, but forms such as paraformaldehyde can also be used, and in addition, part or most of the formaldehyde can be replaced with furfural or furfuryl alcohol. is also possible. Furthermore, as a reaction catalyst, basic substances that generate -NCH2 bonds between the benzene nuclei of phenols, such as hexamethylenetetramine, ammonia, methylamine, dimethylamine, ethylenediamine, monoethanolamine, etc. 1st
and secondary amines can be used. Furthermore, in combination with these, basic catalysts commonly used in the synthesis of phenolic resins, such as alkali metal or alkaline earth metal hydroxides and tertiary amines, can also be used.
【０００９】これらフェノール類とホルムアルデヒド類
及び反応触媒を反応釜など反応容器にとって、フェノー
ル類とホルムアルデヒド類とを反応させるのであるが、
このとき反応容器にさらに黒鉛類の粉末を配合し、この
黒鉛類粉末の存在下でフェノール類とホルムアルデヒド
類との反応をおこなわせる。また、フェノール類とホル
ムアルデヒド類との配合比率は、フェノール類とホルム
アルデヒド類のモル比が１対１〜１対３． ５の範囲で
あるように設定するのが好ましい。[0009] These phenols, formaldehydes, and a reaction catalyst are placed in a reaction vessel such as a reaction pot, and the phenols and formaldehyde are reacted.
At this time, graphite powder is further added to the reaction vessel, and the phenols and formaldehyde are reacted in the presence of the graphite powder. Furthermore, the molar ratio of phenols and formaldehydes is 1:1 to 1:3. It is preferable to set it within the range of 5.
【００１０】また上記のように黒鉛類粉末の存在下でフ
ェノール類とホルムアルデヒド類とを反応させるにあた
って、この反応は反応系を少なくとも撹拌するに足る量
の水の存在下でおこなわれる。このようにして水中で撹
拌しつつ黒鉛類粉末の存在下でフェノール類とホルムア
ルデヒド類とを反応させると、反応の当初では反応系は
粘稠なマヨネーズ状で撹拌に伴って流動する状態である
が、反応が進むにつれて次第に黒鉛類粉末を含むフェノ
ール類とホルムアルデヒド類との縮合反応物が系中の水
と分離し始め、そして反応生成されるフェノール樹脂と
黒鉛類粉末とからなる黒色の粒子が突然に反応容器の全
体に分散される状態になる。このようにフェノール樹脂
と黒鉛類粉末とからなる粒子が突然分散される状態にな
る理由は、黒鉛類は水に対する親和性が小さく反応の初
期においては水中に分散されないが、黒鉛類は六炭素環
が層状に連なった層間化合物であって層間への吸着性が
高く、フェノール類とアルデヒド類との反応の進行に伴
って生成されるフェノール樹脂が黒鉛類の層間へ吸着さ
れることによって黒鉛類はフェノール樹脂との混在物と
して分散されることになり、この黒鉛類粉末とフェノー
ル樹脂との凝集体で黒色の粒子が形成されるのではない
かと考えられる。[0010] Furthermore, in reacting phenols and formaldehydes in the presence of graphite powder as described above, this reaction is carried out in the presence of at least an amount of water sufficient to stir the reaction system. When phenols and formaldehydes are reacted in water in the presence of graphite powder while stirring in this way, at the beginning of the reaction the reaction system is viscous mayonnaise-like and fluid as it is stirred. As the reaction progresses, the condensation reaction product of phenol and formaldehyde containing graphite powder gradually begins to separate from the water in the system, and black particles consisting of phenol resin and graphite powder produced by the reaction suddenly appear. It becomes a state where it is dispersed throughout the reaction vessel. The reason why particles consisting of phenolic resin and graphite powder suddenly become dispersed is that graphite has a small affinity for water and is not dispersed in water at the initial stage of the reaction, but graphite has a six-carbon ring. is an intercalation compound that is connected in a layered manner and has a high adsorption property between the layers, and graphite is It is thought that the graphite powder is dispersed as a mixture with the phenol resin, and black particles are formed by aggregates of the graphite powder and the phenol resin.
【００１１】そしてこのように黒鉛類粉末とフェノール
樹脂との混合黒色粒子が分散生成されたのち、さらに所
望する程度にフェノール樹脂の反応を進めて冷却したの
ちに撹拌を停止すると、この黒色粒子は沈澱して水と分
離される。この黒色粒子は微小な球状粒体となっており
、反応容器から取り出して濾過することによって容易に
分離することができる。これを乾燥することによって、
黒鉛・フェノール樹脂粒状物を得ることができる。
この黒鉛・フェノール樹脂粒状物の粒径は特に限定され
るものではないが、１０μｍ〜２０００μｍ程度の範囲
に調整するのが一般的に望ましい。[0011] After the mixed black particles of graphite powder and phenol resin are dispersed and produced in this way, the reaction of the phenol resin is further advanced to a desired degree, and when stirring is stopped after cooling, the black particles become Separated from water by precipitation. These black particles are in the form of fine spherical particles, and can be easily separated by taking them out of the reaction vessel and filtering them. By drying this
Graphite/phenolic resin granules can be obtained. Although the particle size of the graphite/phenol resin particles is not particularly limited, it is generally desirable to adjust it to a range of about 10 μm to 2000 μm.
【００１２】次に樹脂としてメラミン樹脂を用いる場合
は、樹脂原料としてメラミン類とホルムアルデヒド類と
を使用し、このメラミン類とホルムアルデヒド類を触媒
の存在下で黒鉛類粉末と混合させつつ反応させることに
よって、上記フェノール樹脂の場合と同様にして、黒鉛
・樹脂複合材としての黒鉛・メラミン樹脂粒状物を調製
することができる。メラミン類としてはメラミンやその
誘導体を用いることができ、ホルムアルデヒド類として
は既述したものを用いることができる。触媒としては酸
もしくはアルカリを用いることができる。Next, when using melamine resin as the resin, melamines and formaldehydes are used as resin raw materials, and the melamines and formaldehydes are mixed with graphite powder in the presence of a catalyst and reacted. Graphite/melamine resin granules as a graphite/resin composite material can be prepared in the same manner as in the case of the phenol resin described above. As the melamine, melamine or its derivatives can be used, and as the formaldehyde, those mentioned above can be used. An acid or an alkali can be used as a catalyst.
【００１３】さらに樹脂としてフラン樹脂を用いる場合
は、樹脂原料としてフラン類を使用し、このフラン類を
触媒の存在下で黒鉛類粉末と混合させつつ反応させるこ
とによって、黒鉛・樹脂複合材としての黒鉛・フラン樹
脂複合材を調製することができる。フラン類としてはフ
ルフリルアルコールなどを用いることができるものであ
り、触媒としては酸などを用いることができる。このフ
ラン樹脂の場合は一般的に上記のフェノール樹脂やメラ
ミン樹脂のように球形の粒状の調製できないので、凍結
乾燥等して用いる。Furthermore, when furan resin is used as the resin, furans are used as the resin raw material, and this furan is mixed and reacted with graphite powder in the presence of a catalyst to form a graphite-resin composite material. A graphite-furan resin composite can be prepared. As the furan, furfuryl alcohol or the like can be used, and as the catalyst, an acid or the like can be used. In the case of this furan resin, it is generally not possible to prepare spherical particles like the above-mentioned phenol resins and melamine resins, so it is used by freeze-drying or the like.
【００１４】そして本発明に係る発泡性耐火材料は、上
記のように調製される黒鉛・樹脂複合材に黒鉛層間化合
物を配合して混合することによって得ることができる。
黒鉛層間化合物の配合量は耐火層の所望する発泡倍率（
膨脹倍率）に応じて任意に設定されるものであるが、一
般的には黒鉛・樹脂複合材１００重量部に対して１〜３
０重量部の範囲が好ましい。The foamable fireproof material according to the present invention can be obtained by blending and mixing a graphite intercalation compound with the graphite/resin composite material prepared as described above. The blending amount of the graphite intercalation compound is determined by the desired expansion ratio (
Although it is arbitrarily set depending on the expansion ratio (expansion ratio), it is generally 1 to 3 parts by weight per 100 parts by weight of graphite/resin composite material.
A range of 0 parts by weight is preferred.
【００１５】以上のようにして得られる本発明に係る発
泡性耐火材料は、樹脂をバインダーとして含有するため
に成形性が良好であり、これを射出成形、圧縮成形、移
送成形、押出し成形など任意の方法で成形して用いるこ
とができるものであり、例えばシート状に成形して平板
状に形成し、これを扉や壁などの表面若しくは内部に張
ることによって耐火扉や耐火壁などを作成することがで
きる。また耐火扉の上下及び左右の端面に張ってシール
材として使用することもできる。さらに建築物の室内の
床面に張ったり天井面に張ったりすることもできる。The foamable fireproof material according to the present invention obtained as described above has good moldability because it contains resin as a binder, and can be molded by any method such as injection molding, compression molding, transfer molding, or extrusion molding. For example, by forming a sheet into a flat plate and applying it to the surface or inside of a door or wall, a fire-resistant door or wall can be created. be able to. It can also be used as a sealing material by applying it to the top, bottom, left and right end surfaces of a fireproof door. Furthermore, it can also be placed on the floor or ceiling inside a building.
【００１６】[0016]
【作用】上記ように本発明に係る発泡性耐火材料を成形
して得られる耐火層は、黒鉛を充填剤として含有してい
るために高い耐熱性を有しており、火災時に火炎にさら
されても十分に耐えて火炎が広がることを遮断すること
ができるものである。またこの火災時には高温が耐火層
に作用するために、耐火層中の黒鉛層間化合物が膨脹し
て耐火層は発泡状態になって膨脹することになる。従っ
て耐火層に局所的に火炎や高温が作用してこの部分に亀
裂等が発生しても、耐火層の膨脹によってこの亀裂によ
る隙間は閉じられることになり、亀裂の隙間から火炎が
侵入したり煙が侵入したりすることを防ぐことができる
ものである。特に耐火層を上記のように耐火扉の上下及
び左右の端面に張ってシール材として使用する場合、耐
火層はこのように発泡して膨脹するために扉の端面と扉
が閉じている開口部との間の隙間にこの耐火層が充填さ
れることになり、扉の端面と開口部との間から煙や有毒
ガスが侵入することを防ぐことができることになる。[Function] As mentioned above, the fireproof layer obtained by molding the foamable fireproof material according to the present invention has high heat resistance because it contains graphite as a filler, and is not exposed to flame in the event of a fire. It is able to withstand fires sufficiently and prevent the spread of flames. Further, in the event of a fire, high temperatures act on the fireproof layer, so that the graphite intercalation compound in the fireproof layer expands, causing the fireproof layer to become foamed and expand. Therefore, even if flames or high temperatures act locally on the fireproof layer and cracks occur in this area, the expansion of the fireproof layer closes the gaps caused by the cracks, preventing flames from penetrating through the cracks. This can prevent smoke from entering. In particular, when using the fireproof layer as a sealant by applying it to the top and bottom, left and right end faces of a fireproof door as described above, the fireproof layer foams and expands in this way, so the fireproof layer is applied to the end faces of the door and the opening where the door is closed. This refractory layer fills the gap between the door and the opening, thereby preventing smoke and toxic gas from entering between the end face of the door and the opening.
【００１７】また本発明に係る発泡性耐火材をシート状
に成形して得られる耐火層は黒鉛を充填剤として含有す
るために導電性を有しており、電磁波をシールドする効
果及び静電気をアースして除去する効果を有する。特に
請求項２に記載の発泡性耐火材料は電磁波に対して低い
周波数から高い周波数に亘って優れたシールド効果を発
揮する。すなわち、請求項１に記載の発泡性耐火材料の
ように樹脂に黒鉛類粉末をニーダー等で単に混入するこ
とによって調製した材料を用いるようにしたものは、４
００〜５００ＭＨｚ 以下の低い周波数の電磁波や、６
００〜７００ＭＨｚ 以上の高い周波数の電磁波をシー
ルドする効果が十分ではないが、請求項２に記載の発泡
性耐火材料はこれらの周波数においても電磁波のシール
ド効果を高く得ることができる。その理由は明確ではな
いが、黒鉛類粉末を単に樹脂に混入して用いる場合は、
黒鉛類粉末と樹脂との濡れ性等が十分でないために均一
に黒鉛類粉末を分散させることが難しいが、樹脂原料を
触媒の存在下で反応させる際に黒鉛類粉末を混合して調
製することによって、黒鉛類粉末を均一に分散させるこ
とが容易であり、シールド効果の差異はこの黒鉛類粉末
の分散の均一性に起因するのではないかと考えられる。Furthermore, the fireproof layer obtained by molding the foamable fireproof material according to the present invention into a sheet form contains graphite as a filler and therefore has conductivity, and has the effect of shielding electromagnetic waves and grounding static electricity. It has the effect of removing. In particular, the foamable refractory material according to claim 2 exhibits an excellent shielding effect against electromagnetic waves from low frequencies to high frequencies. That is, the foamable fireproof material according to claim 1, which uses a material prepared by simply mixing graphite powder into a resin using a kneader, etc.
Low frequency electromagnetic waves of 00 to 500MHz or less,
Although the effect of shielding electromagnetic waves at high frequencies of 00 to 700 MHz or more is not sufficient, the foamable fireproof material according to claim 2 can obtain a high electromagnetic wave shielding effect even at these frequencies. The reason for this is not clear, but when graphite powder is simply mixed into resin and used,
It is difficult to uniformly disperse graphite powder due to insufficient wettability between graphite powder and resin, but it can be prepared by mixing graphite powder when reacting resin raw materials in the presence of a catalyst. This makes it easy to uniformly disperse the graphite powder, and it is thought that the difference in shielding effect is due to the uniformity of the graphite powder dispersion.
【００１８】[0018]
【実施例】次に、本発明を実施例によって例証する。
実施例１
（黒鉛・フェノール樹脂複合材の調製）ニーダーに平均
粒径５μｍの天然鱗片状黒鉛を１１００重量部、数平均
分子量３５０の固形レゾール型フェノール樹脂の６０％
メタノール溶液を１１１０重量部を投入し、正転・反転
を繰り返して約３０分間混練をおこなった。次にこれを
ニーダーから払い出した後、風乾によりメタノールを蒸
発させて乾燥し、これを粉砕機にかけて１ｍｍ以下の粒
径に粗粉砕をおこなうことによって、自硬性の黒鉛・フ
ェノール樹脂複合材を得た。この黒鉛・フェノール樹脂
複合材は、黒鉛の含有率が６０重量％、フェノール樹脂
の含有率が４０重量％であった。EXAMPLES The present invention will now be illustrated by examples. Example 1 (Preparation of graphite/phenolic resin composite material) In a kneader, 1100 parts by weight of natural flaky graphite with an average particle size of 5 μm and 60% of a solid resol type phenol resin with a number average molecular weight of 350 were added.
1110 parts by weight of methanol solution was added, and kneading was performed for about 30 minutes by repeating forward and reverse rotation. Next, after discharging this from the kneader, it was dried by air drying to evaporate the methanol, and was coarsely ground to a particle size of 1 mm or less using a grinder, thereby obtaining a self-hardening graphite/phenol resin composite material. . This graphite/phenolic resin composite material had a graphite content of 60% by weight and a phenolic resin content of 40% by weight.
【００１９】（黒鉛層間化合物の調製）反応容器に平均
粒径が６μｍ、固定炭素量が８７％の天然鱗片状黒鉛を
１０００重量部入れ、これに９８％濃度の濃硫酸を２０
００重量部加えて濃硫酸に黒鉛を良く浸漬させ、次にこ
れに５８％濃度の硝酸を添加して３０分間攪拌混合し、
そしてこれを水洗して乾燥することによって黒鉛層間化
合物を得た。(Preparation of graphite intercalation compound) 1000 parts by weight of natural flaky graphite with an average particle size of 6 μm and a fixed carbon content of 87% is placed in a reaction vessel, and 20 parts by weight of concentrated sulfuric acid with a concentration of 98% is added to the reactor.
00 parts by weight was added and the graphite was well immersed in concentrated sulfuric acid, then 58% nitric acid was added thereto and mixed with stirring for 30 minutes.
Then, this was washed with water and dried to obtain a graphite intercalation compound.
【００２０】上記のようにして調製した黒鉛・フェノー
ル樹脂複合材と黒鉛層間化合物とを、９８：２（実施例
１−１）、９６：４（実施例１−２）、９４：６（実施
例１−３）、９０：１０（実施例１−４）、８５：１５
（実施例１−５）、８０：２０（実施例１−６）の重量
比で配合して混合した後に、高速ミキシングマシンで５
分間混合攪拌することによって発泡性耐火材料を調製し
た。[0020] The graphite/phenolic resin composite material prepared as described above and the graphite intercalation compound were mixed at 98:2 (Example 1-1), 96:4 (Example 1-2), and 94:6 (Example 1-2). Example 1-3), 90:10 (Example 1-4), 85:15
(Example 1-5) and 80:20 (Example 1-6).
A foamable refractory material was prepared by mixing and stirring for a minute.
【００２１】実施例２
（黒鉛・フェノール樹脂複合材の調製）反応容器に平均
粒径が５μｍの天然鱗片状黒鉛を１１００重量部、フェ
ノールを７７０重量部、３７％ホルマリンを１３２８重
量部、反応触媒としてヘキサメチレンテトラミンを８０
重量部仕込むと共に、さらに水を８０重量部仕込み、こ
れを混合撹拌しつつ６０分を要して９０℃まで昇温して
そのまま３時間反応を維持した。このように反応させる
ことによって黒鉛とフェノール樹脂とからなる黒色粒状
物が反応系に生成された。冷却後この黒色粒状物を濾別
して乾燥することによって、自硬性の黒鉛・フェノール
樹脂複合材を得た。この黒鉛・フェノール樹脂複合材は
平均粒径が１５０μｍであり、黒鉛の含有率が６０重量
％、フェノール樹脂の含有率が４０重量％であった。Example 2 (Preparation of graphite/phenolic resin composite material) In a reaction vessel, 1100 parts by weight of natural flaky graphite with an average particle size of 5 μm, 770 parts by weight of phenol, 1328 parts by weight of 37% formalin, and a reaction catalyst were placed. Hexamethylenetetramine as 80
At the same time, 80 parts by weight of water was further added, and the mixture was heated to 90° C. over 60 minutes while being mixed and stirred, and the reaction was maintained for 3 hours. By reacting in this manner, black particulate matter consisting of graphite and phenol resin was produced in the reaction system. After cooling, the black granules were filtered and dried to obtain a self-hardening graphite/phenol resin composite material. This graphite/phenolic resin composite material had an average particle size of 150 μm, a graphite content of 60% by weight, and a phenolic resin content of 40% by weight.
【００２２】上記のようにして調製した黒鉛・フェノー
ル樹脂複合材と実施例１で調製した黒鉛層間化合物とを
、９８：２（実施例２−１）、９６：４（実施例２−２
）、９４：６（実施例２−３）、９０：１０（実施例２
−４）、８５：１５（実施例２−５）、８０：２０（実
施例２−６）の重量比で配合して混合した後に、高速ミ
キシングマシンで５分間混合攪拌することによって発泡
性耐火材料を調製した。The graphite/phenolic resin composite material prepared as described above and the graphite intercalation compound prepared in Example 1 were mixed at 98:2 (Example 2-1) and 96:4 (Example 2-2).
), 94:6 (Example 2-3), 90:10 (Example 2
-4), 85:15 (Example 2-5), and 80:20 (Example 2-6), and then mixed and stirred for 5 minutes with a high-speed mixing machine to form a fire-resistant foam. Materials were prepared.
【００２３】実施例３
（黒鉛・フェノール樹脂複合材の調製）反応容器に平均
粒径が５μｍの鱗片状黒鉛を１１００重量部、フェノー
ルを２００重量部、３７％ホルマリンを３４０重量部、
反応触媒としてヘキサメチレンテトラミンを２２重量部
仕込み、あとは実施例２の場合と同様にして反応させる
ことによって、平均粒径が７５μｍ、黒鉛の含有率が９
０重量％、フェノール樹脂の含有率が１０重量％の自硬
性の黒鉛・フェノール樹脂複合材を得た。Example 3 (Preparation of graphite/phenolic resin composite material) In a reaction vessel, 1100 parts by weight of flaky graphite with an average particle size of 5 μm, 200 parts by weight of phenol, 340 parts by weight of 37% formalin,
By adding 22 parts by weight of hexamethylenetetramine as a reaction catalyst and carrying out the reaction in the same manner as in Example 2, the average particle size was 75 μm and the graphite content was 9.
A self-hardening graphite/phenol resin composite material with a phenolic resin content of 0% by weight and a phenolic resin content of 10% by weight was obtained.
【００２４】このようにして調製した黒鉛・フェノール
樹脂複合材と実施例１で調製した黒鉛層間化合物とを、
９５：５（実施例３−１）、９０：１０（実施例３−２
）、８０：２０（実施例３−３）の重量比で配合して実
施例１と同様に混合攪拌することによって発泡性耐火材
料を調製した。
実施例４
（黒鉛・メラミン樹脂複合材の調製）反応容器に平均粒
径が５μｍの鱗片状黒鉛を１１００重量部、メラミンを
７５０重量部、３７％ホルマリンを９６０重量部、水を
１１５０重量部、反応触媒として蟻酸を１１重量部仕込
み、約３０分を要して７０℃まで昇温させてそのまま２
４０分間反応させることによって、平均粒径が７５μｍ
、黒鉛の含有率が５８．５重量％、メラミン樹脂の含有
率が４１．５重量％の自硬性の黒鉛・メラミン樹脂複合
材を得た。[0024] The graphite/phenolic resin composite material thus prepared and the graphite intercalation compound prepared in Example 1 were
95:5 (Example 3-1), 90:10 (Example 3-2)
) and 80:20 (Example 3-3) in a weight ratio and mixed and stirred in the same manner as in Example 1 to prepare a foamable fireproof material. Example 4 (Preparation of graphite/melamine resin composite material) In a reaction vessel, 1100 parts by weight of flaky graphite with an average particle size of 5 μm, 750 parts by weight of melamine, 960 parts by weight of 37% formalin, 1150 parts by weight of water, 11 parts by weight of formic acid was added as a reaction catalyst, and the temperature was raised to 70°C over about 30 minutes.
By reacting for 40 minutes, the average particle size was 75 μm.
A self-hardening graphite/melamine resin composite material having a graphite content of 58.5% by weight and a melamine resin content of 41.5% by weight was obtained.
【００２５】このようにして調製した黒鉛・メラミン樹
脂複合材と実施例１で調製した黒鉛層間化合物とを８０
：２０の重量比で配合して実施例１と同様に混合攪拌す
ることによって発泡性耐火材料を調製した。
実施例５
（黒鉛・フラン樹脂複合材の調製）反応容器に平均粒径
が５μｍの鱗片状黒鉛を１１００重量部、フルフリルア
ルコールを９８０重量部、３７％ホルマリンを４０５重
量部、水を５００重量部、さらに反応触媒として１０％
リン酸水溶液を３０重量部仕込み、これを混合撹拌しな
がら還流下で１８０分間反応をおこなった。このものを
冷却後水を分離したのちに凍結乾燥をおこない、若干粘
着性のある自硬性の黒鉛・フラン樹脂複合材を得た。こ
のものは黒鉛の含有率が６１． ８重量％、フラン樹脂
の含有率が３８． ２重量％であった。The graphite/melamine resin composite thus prepared and the graphite intercalation compound prepared in Example 1 were mixed at 80%
:20 weight ratio and mixed and stirred in the same manner as in Example 1 to prepare a foamable fireproof material. Example 5 (Preparation of graphite/furan resin composite material) In a reaction vessel, 1100 parts by weight of flaky graphite with an average particle size of 5 μm, 980 parts by weight of furfuryl alcohol, 405 parts by weight of 37% formalin, and 500 parts by weight of water were placed in a reaction vessel. part, plus 10% as a reaction catalyst
30 parts by weight of an aqueous phosphoric acid solution was charged, and the mixture was mixed and stirred to carry out a reaction under reflux for 180 minutes. This material was cooled, water was separated, and then freeze-dried to obtain a slightly sticky self-hardening graphite/furan resin composite material. This material has a graphite content of 61. 8% by weight, and the content of furan resin is 38. It was 2% by weight.
【００２６】このようにして調製した黒鉛・フラン樹脂
複合材と実施例１で調製した黒鉛層間化合物とを８０：
２０の重量比で配合して実施例１と同様に混合攪拌する
ことによって発泡性耐火材料を調製した。上記のように
して得た実施例１乃至実施例５の発泡性耐火材を、予め
１６０℃に加熱した金型の縦１５０ｍｍ×横７０ｍｍの
大きさの開口のキャビティに入れ、１０分間加熱して硬
化させることによって、比重が１．５で厚みが３〜４ｍ
ｍのシート状の試験片を成形した。また比較のために、
黒鉛層間化合物を配合しないで黒鉛・樹脂複合材のみを
用いて同様に試験片を成形した（実施例１〜５に対応し
て比較例１〜５とする）。これらの試験片について電磁
波シールド性能を測定した。測定は「ＡＳＴＭ ＥＳ
７−８３」に準拠したＤｕａｌ Ｃｈａｍｂｅｒ法（
近接電界法）によって電磁波の透過損失を計測すること
によっておこなった。次に、この測定後の試験片を縦５
０ｍｍ×横５０ｍｍの大きさに切断し、表面抵抗率と体
積抵抗率を測定した。結果をそれぞれの表に示す。The graphite/furan resin composite thus prepared and the graphite intercalation compound prepared in Example 1 were mixed at 80:
A foamable refractory material was prepared by mixing and stirring in the same manner as in Example 1 by blending the materials at a weight ratio of 20. The foamable refractory materials of Examples 1 to 5 obtained as described above were placed in a cavity with an opening measuring 150 mm long x 70 mm wide in a mold preheated to 160°C, and heated for 10 minutes. By curing, the specific gravity is 1.5 and the thickness is 3 to 4 m.
A sheet-like test piece of m was molded. Also, for comparison,
Test pieces were similarly molded using only the graphite/resin composite material without blending the graphite intercalation compound (Comparative Examples 1 to 5 correspond to Examples 1 to 5). The electromagnetic shielding performance of these test pieces was measured. Measurements are made using ASTM ES
7-83” Dual Chamber method (
This was done by measuring the transmission loss of electromagnetic waves using the near field method. Next, the test piece after this measurement was
It was cut into a size of 0 mm x width 50 mm, and the surface resistivity and volume resistivity were measured. The results are shown in the respective tables.
【００２７】また上記実施例１乃至５及び比較例１乃至
５の材料を、予め１６０℃に加熱した金型の縦１００ｍ
ｍ×横１００ｍｍの大きさの開口のキャビティに入れ、
１０分間加熱して硬化させることによって、比重が１．
５で厚みが５ｍｍのシート状の試験片を成形し、これを
さらに幅２０ｍｍで切断して曲げ強さ及び曲げ弾性率の
測定に供し、さらにロックウェル硬度を測定した。結果
をそれぞれの表に示す。[0027] The materials of Examples 1 to 5 and Comparative Examples 1 to 5 were placed in a mold of 100 m in length that had been preheated to 160°C.
Put it into a cavity with an opening size of m x width 100 mm,
By heating and curing for 10 minutes, the specific gravity becomes 1.
A sheet-like test piece having a thickness of 5 mm was formed using No. 5, and this was further cut into a width of 20 mm to measure bending strength and bending elastic modulus, and Rockwell hardness was also measured. The results are shown in the respective tables.
【００２８】さらにこの厚み５ｍｍの試験片を縦２０ｍ
ｍ×横２０ｍｍの大きさに切断し、発泡試験に供した。
発泡試験は、この切断した試験片を直径３０ｍｍの試験
管に入れ、これを予め３００℃、４００℃、５００℃、
６００℃、７００℃に加熱した電気炉に入れて１０分間
保持した後に取り出し、加熱発泡させる前と加熱発泡さ
せた後の試験片の容積変化を測定することによっておこ
ない、結果を発泡倍率としてそれぞれの表に示す。[0028] Furthermore, this test piece with a thickness of 5 mm was
It was cut into a size of m x width 20 mm and subjected to a foaming test. For the foaming test, the cut test piece was placed in a test tube with a diameter of 30 mm, and the test tube was heated at 300°C, 400°C, 500°C,
The test piece was placed in an electric furnace heated to 600°C or 700°C, held for 10 minutes, then taken out, and the volume change of the specimen was measured before and after heating and foaming, and the results were used as the foaming ratio for each. Shown in the table.
【００２９】[0029]
【表１】[Table 1]
【００３０】[0030]
【表２】[Table 2]
【００３１】[0031]
【表３】[Table 3]
【００３２】[0032]
【表４】[Table 4]
【００３３】[0033]
【表５】[Table 5]
【００３４】[0034]
【表６】[Table 6]
【００３５】[0035]
【表７】[Table 7]
【００３６】前記の各表の結果にみられるように、黒鉛
層間化合物を配合した実施例１〜５の材料で作成した耐
火層は高温の作用で発泡して膨脹することが確認される
。また、電磁波シールド効果が高いことが確認されると
共に、表面抵抗率や体積抵抗率は１０３ のレベルより
も小さく静電気をアースする性能が高いことも確認され
る。さらに曲げ強さ及び曲げ弾性率はいずれも高く、耐
火扉や耐火壁の耐火層として使用するにあたって扉や壁
の強度を高めることができるものである。As can be seen from the results in the above tables, it is confirmed that the fireproof layers made of the materials of Examples 1 to 5 containing graphite intercalation compounds foam and expand under the action of high temperatures. It is also confirmed that the electromagnetic wave shielding effect is high, and that the surface resistivity and volume resistivity are lower than the 103 level, and the performance for grounding static electricity is high. Furthermore, both the bending strength and the bending elastic modulus are high, and when used as a fireproof layer for fireproof doors and fireproof walls, the strength of the doors and walls can be increased.
【００３７】[0037]
【発明の効果】上記のように本発明は、黒鉛・樹脂複合
材に黒鉛層間化合物を配合してあるので、黒鉛を充填剤
として含有していて高い耐熱性を有する耐火層を得るこ
とができると共にまた火災時の高温の作用で黒鉛層間化
合物が膨脹して耐火層は発泡状態になって膨脹し、耐火
層に亀裂等が発生しても耐火層の膨脹によってこの亀裂
による隙間が閉じて亀裂の隙間から火炎が侵入したり煙
が侵入したりすることを防ぐことができるものである。
さらに、本発明に係る発泡性耐火材をシート状に成形し
て得られる耐火層は黒鉛を充填剤として含有するために
導電性を有しており、電磁波障害や静電気障害に対処す
ることもできるものである。加えて、本発明に係る発泡
性耐火材は樹脂をバインダーとして含有するために、シ
ート状に成形することによって容易に耐火層を形成する
ことができるものである。[Effects of the Invention] As described above, in the present invention, since a graphite intercalation compound is blended into a graphite/resin composite material, a fireproof layer containing graphite as a filler and having high heat resistance can be obtained. At the same time, the graphite intercalation compound expands due to the action of high temperatures during a fire, and the fireproof layer becomes foamy and expands. Even if a crack occurs in the fireproof layer, the gap caused by this crack closes due to the expansion of the fireproof layer, causing the crack to disappear. This prevents flames and smoke from entering through the gaps. Furthermore, the fireproof layer obtained by molding the foamable fireproofing material according to the present invention into a sheet form contains graphite as a filler and therefore has conductivity, and can also deal with electromagnetic interference and static electricity interference. It is something. In addition, since the foamable fireproof material according to the present invention contains a resin as a binder, it can be easily formed into a sheet to form a fireproof layer.
Claims (6)
れる黒鉛・樹脂複合材と、黒鉛層間化合物とを配合して
成ることを特徴とする発泡性耐火材料。1. A foamable fireproof material comprising a graphite/resin composite prepared by mixing a resin and graphite powder, and a graphite intercalation compound.
反応させて調製される黒鉛・樹脂複合材と、黒鉛層間化
合物とを配合して成ることを特徴とする発泡性耐火材料
。2. A foamable fireproof material comprising a graphite-resin composite prepared by mixing a resin raw material with graphite powder and reacting the same, and a graphite intercalation compound.
間に硫酸が挿入されたものであることを特徴とする請求
項１又は２に記載の発泡性耐火材料。3. The foamable refractory material according to claim 1 or 2, wherein the graphite intercalation compound is one in which sulfuric acid is inserted between layers of graphite layered crystals.
デヒド類であり、黒鉛・樹脂複合材が黒鉛・フェノール
樹脂粒状物であることを特徴とする請求項２又は３に記
載の発泡性耐火材料。4. The foamable fireproof material according to claim 2 or 3, wherein the resin raw materials are phenols and formaldehydes, and the graphite/resin composite material is graphite/phenol resin granules.
ヒド類であり、黒鉛・樹脂複合材が黒鉛・メラミン樹脂
粒状物であることを特徴とする請求項２又は３に記載の
発泡性耐火材料。5. The foamable fireproof material according to claim 2, wherein the resin raw materials are melamines and formaldehydes, and the graphite/resin composite material is graphite/melamine resin granules.
脂複合材が黒鉛・フラン樹脂複合材であることを特徴と
する請求項２又は３に記載の発泡性耐火材料。6. The foamable fireproof material according to claim 2 or 3, wherein the resin raw material is furan, and the graphite/resin composite material is a graphite/furan resin composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11594391A JPH04342764A (en) | 1991-05-21 | 1991-05-21 | Foamable fire-resisting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11594391A JPH04342764A (en) | 1991-05-21 | 1991-05-21 | Foamable fire-resisting material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04342764A true JPH04342764A (en) | 1992-11-30 |
Family
ID=14675015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11594391A Pending JPH04342764A (en) | 1991-05-21 | 1991-05-21 | Foamable fire-resisting material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04342764A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1347011A1 (en) * | 2002-03-21 | 2003-09-24 | Alcatel | Cable sheath comprising a non halogenated flame retardant composition |
| CN100419028C (en) * | 2005-11-14 | 2008-09-17 | 南京理工大学 | Polymjer base functional composite material with fire-resistant and conducting function |
-
1991
- 1991-05-21 JP JP11594391A patent/JPH04342764A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1347011A1 (en) * | 2002-03-21 | 2003-09-24 | Alcatel | Cable sheath comprising a non halogenated flame retardant composition |
| FR2837494A1 (en) * | 2002-03-21 | 2003-09-26 | Cit Alcatel | NON-HALLOGENATED INTUMESCENT COMPOSITION FOR TELECOMMUNICATION CABLE SHEATH |
| US6998536B2 (en) | 2002-03-21 | 2006-02-14 | Alcatel | Cable sheath including a halogen-free intumescent composition |
| CN100419028C (en) * | 2005-11-14 | 2008-09-17 | 南京理工大学 | Polymjer base functional composite material with fire-resistant and conducting function |
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| A02 | Decision of refusal |
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