JP2020189415A - Fireproof multilayer sheet - Google Patents
Fireproof multilayer sheet Download PDFInfo
- Publication number
- JP2020189415A JP2020189415A JP2019094773A JP2019094773A JP2020189415A JP 2020189415 A JP2020189415 A JP 2020189415A JP 2019094773 A JP2019094773 A JP 2019094773A JP 2019094773 A JP2019094773 A JP 2019094773A JP 2020189415 A JP2020189415 A JP 2020189415A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- resin
- multilayer sheet
- heat
- expandable
- 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.)
- Granted
Links
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- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 4
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- 239000004566 building material Substances 0.000 description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 3
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- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
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- 239000011230 binding agent Substances 0.000 description 2
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MJUJXFBTEFXVKU-UHFFFAOYSA-N diethyl phosphonate Chemical compound CCOP(=O)OCC MJUJXFBTEFXVKU-UHFFFAOYSA-N 0.000 description 1
- YLFBFPXKTIQSSY-UHFFFAOYSA-N dimethoxy(oxo)phosphanium Chemical compound CO[P+](=O)OC YLFBFPXKTIQSSY-UHFFFAOYSA-N 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- PLSFNSJUKGEOSL-UHFFFAOYSA-N dioctoxy(oxo)phosphanium Chemical compound CCCCCCCCO[P+](=O)OCCCCCCCC PLSFNSJUKGEOSL-UHFFFAOYSA-N 0.000 description 1
- HAKMAMKAFTZXOZ-UHFFFAOYSA-N dioctoxyphosphorylbenzene Chemical compound CCCCCCCCOP(=O)(OCCCCCCCC)C1=CC=CC=C1 HAKMAMKAFTZXOZ-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NXHKQBCTZHECQF-UHFFFAOYSA-N ethyl(methyl)phosphinic acid Chemical compound CCP(C)(O)=O NXHKQBCTZHECQF-UHFFFAOYSA-N 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- SZTJCIYEOQYVED-UHFFFAOYSA-N methyl(propyl)phosphinic acid Chemical compound CCCP(C)(O)=O SZTJCIYEOQYVED-UHFFFAOYSA-N 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- NSETWVJZUWGCKE-UHFFFAOYSA-N propylphosphonic acid Chemical compound CCCP(O)(O)=O NSETWVJZUWGCKE-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- OGDSVONAYZTTDA-UHFFFAOYSA-N tert-butylphosphonic acid Chemical compound CC(C)(C)P(O)(O)=O OGDSVONAYZTTDA-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Building Environments (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は耐火多層シートに関し、特に、粉体塗装等の塗装が施される耐火多層シートに関する。 The present invention relates to a refractory multilayer sheet, and more particularly to a refractory multilayer sheet to which a coating such as powder coating is applied.
建築材料の分野において、耐火性能を有する樹脂材料が求められており、そのような材料として、バインダー（樹脂）と熱膨張性黒鉛とを含む熱膨張材が知られている。 In the field of building materials, a resin material having fire resistance is required, and as such a material, a heat-expanding material containing a binder (resin) and heat-expandable graphite is known.
熱膨張材は、目視可能な部分に取付けられることがあり、その際には熱膨張材の外観を、取り付けられる場所の色と合わせたり意匠性を付与したりするために塗料等で塗装することがある。
例えば、特許文献１では、バインダー樹脂と熱膨張性黒鉛とを含む熱膨張性樹脂組成物からなる熱膨張材と、熱膨張材に積層された基材とを備え、熱膨張材と基材との間に熱可塑性樹脂を含有する介在層が配置されている耐火多層シートが開示されている。
The thermal expansion material may be attached to a visible part, in which case the appearance of the thermal expansion material should be painted with paint to match the color of the place where it is attached or to give it a design. There is.
For example, in Patent Document 1, a heat-expandable material made of a heat-expandable resin composition containing a binder resin and heat-expandable graphite, and a base material laminated on the heat-expandable material are provided, and the heat-expandable material and the base material are provided. A refractory multilayer sheet in which an interposition layer containing a thermoplastic resin is arranged between the two is disclosed.
ところで、塗料等で塗装する方法は種々あるが、なかでも粉体塗装は、溶剤の代わりに空気を用いるので溶剤による火災及び毒性の危険がなく、塗装機の自動化が容易なため塗膜品質が安定する等といったメリットがあり、耐火多層シートに対してもその適用が検討されている。 By the way, there are various methods of painting with paints, etc. Among them, powder coating uses air instead of solvent, so there is no risk of fire and toxicity due to the solvent, and the coating quality is easy to automate. It has merits such as stability, and its application to fireproof multilayer sheets is also being considered.
耐火多層シートの構成として、例えば、熱膨張材からなる熱膨張樹脂層の上下それぞれをポリエチレン等の接着層を介して不織布で両面を挟んだものが挙げられる。このような耐火多層シートに対し粉体塗装を行うと、その後の焼き付けで不織布が脱落してしまう問題があった。 Examples of the structure of the refractory multilayer sheet include those in which both upper and lower sides of a heat-expandable resin layer made of a heat-expandable material are sandwiched between non-woven fabrics via an adhesive layer such as polyethylene. When powder coating is applied to such a refractory multilayer sheet, there is a problem that the non-woven fabric falls off in the subsequent baking.
そこで本発明者らは、脱落が起こらないように、上記の不織布及び接着層を、ポリエステル（具体的にはＰＥＴ：ポリエチレンテレフタレート）で代替することを考えた。しかし、通常のＰＥＴを使用する場合、耐火多層シートを作製する際、あるいは耐火多層シートに粉末塗装をする際にゴム製のコンベアベルトで当該ＰＥＴを搬送するが、このＰＥＴと搬送する際のコンベアベルトとの摩擦が大きくなり、搬送性が低下する問題が生じた。 Therefore, the present inventors have considered replacing the above-mentioned non-woven fabric and adhesive layer with polyester (specifically, PET: polyethylene terephthalate) so as not to cause falling off. However, when a normal PET is used, the PET is conveyed by a rubber conveyor belt when the fire-resistant multilayer sheet is produced or when the fire-resistant multilayer sheet is powder-coated. There was a problem that the friction with the belt became large and the transportability was lowered.
以上から、本発明では、ゴム製のコンベアベルトに対し良好な搬送性を発揮し得る耐火多層シートを提供することを課題とする。 From the above, it is an object of the present invention to provide a refractory multilayer sheet capable of exhibiting good transportability for a rubber conveyor belt.
上記課題を解決すべく鋭意検討した結果、本発明者らは、ゴム製のコンベアベルトに接触する耐火多層シートの基材表面の表面粗さを特定の範囲に小さくすることで、摩擦が低減して搬送性が良好になることを見出し、本発明を完成させた。
すなわち、本発明は下記のとおりである。
As a result of diligent studies to solve the above problems, the present inventors reduced the surface roughness of the base material surface of the fireproof multilayer sheet in contact with the rubber conveyor belt within a specific range, thereby reducing friction. The present invention has been completed by finding that the transportability is improved.
That is, the present invention is as follows.
［１］ 第１の基材と熱膨張樹脂層と第２の基材とをこの順に備える耐火多層シートであって、前記熱膨張樹脂層が樹脂及び熱膨張性黒鉛を含み、第１の基材における前記熱膨張樹脂層が設けられていない側の面の表面粗さＲａが、０．２μｍ〜５０μｍである耐火多層シート。
［２］ 第２の基材が白色である［１］に記載の耐火多層シート。
［３］ 第１の基材及び第２の基材の軟化点が２００℃以上である［１］又は［２］に記載の耐火多層シート。
［４］ 前記樹脂が熱硬化性樹脂を含む［１］〜［３］のいずれかに記載の耐火多層シート。
［５］ 第１の基材における前記熱膨張樹脂層が設けられていない側の面に粘着剤及びセパレータの少なくともいずれかを備える［１］〜［４］のいずれかに記載の耐火多層シート。
［６］ 第２の基材における前記熱膨張樹脂層が設けられていない側の面の表面粗さＲａが、０．５μｍ以下である［１］〜［５］のいずれかに記載の耐火多層シート。
[1] A refractory multilayer sheet comprising a first base material, a heat-expandable resin layer, and a second base material in this order, wherein the heat-expandable resin layer contains a resin and heat-expandable graphite, and is a first group. A refractory multilayer sheet having a surface roughness Ra of 0.2 μm to 50 μm on the surface of the material on which the thermal expansion resin layer is not provided.
[2] The refractory multilayer sheet according to [1], wherein the second base material is white.
[3] The refractory multilayer sheet according to [1] or [2], wherein the first base material and the second base material have a softening point of 200 ° C. or higher.
[4] The refractory multilayer sheet according to any one of [1] to [3], wherein the resin contains a thermosetting resin.
[5] The refractory multilayer sheet according to any one of [1] to [4], which comprises at least one of an adhesive and a separator on the surface of the first base material on the side where the thermal expansion resin layer is not provided.
[6] The refractory multilayer according to any one of [1] to [5], wherein the surface roughness Ra of the surface of the second base material on the side where the thermal expansion resin layer is not provided is 0.5 μm or less. Sheet.
本発明によれば、ゴム製のコンベアベルトに対し良好な搬送性を発揮し得る耐火多層シートを提供することができる。 According to the present invention, it is possible to provide a refractory multilayer sheet capable of exhibiting good transportability for a rubber conveyor belt.
＜耐火多層シート＞
図１に示すように、本発明の一実施形態に係る耐火多層シート１０は、第１の基材１２と熱膨張樹脂層１４と第２の基材１６とをこの順に備え、熱膨張樹脂層１４が樹脂及び熱膨張性黒鉛を含み、第１の基材１２における熱膨張樹脂層１４が設けられていない側の面１２Ａの表面粗さＲａが、０．２μｍ〜５０μｍ以下となっている。以下、本発明の耐火多層シートについて詳細に説明する。
<Fireproof multilayer sheet>
As shown in FIG. 1, the refractory multilayer sheet 10 according to the embodiment of the present invention includes a first base material 12, a heat-expandable resin layer 14, and a second base material 16 in this order, and is provided with a heat-expandable resin layer. 14 contains a resin and heat-expandable graphite, and the surface roughness Ra of the surface 12A on the side of the first base material 12 on which the heat-expandable resin layer 14 is not provided is 0.2 μm to 50 μm or less. Hereinafter, the refractory multilayer sheet of the present invention will be described in detail.
（第１の基材）
第１の基材の熱膨張樹脂層が設けられていない側の面の表面粗さＲａは０．２μｍ〜５０μｍとなっている。Ｒａが０．２μｍ未満では、ゴム製のコンベアベルトと、これに接触する耐火多層シートの基材表面と摩擦力が大きくなり良好な搬送性が得られない。５０μｍを超えると、上記摩擦力が低くなりすぎて位置固定がしづらくなる等の問題が生じやすくなる。Ｒａは０．４μｍ以上であることが好ましく、０．５μｍ以上であることがより好ましい。また、１０μｍ以下であることが好ましく、５μｍ以下であることがより好ましい。表面粗さＲａは実施例に記載の方法で測定することができる。
なお、表面粗さを上記範囲のように小さくすることで、第１の基材の熱膨張樹脂層が設けられていない側に粘着剤を付与させやすくなり、耐火多層シートに良好な粘着機能を持たせることができる。
(First base material)
The surface roughness Ra of the surface of the first base material on the side where the thermal expansion resin layer is not provided is 0.2 μm to 50 μm. If Ra is less than 0.2 μm, the frictional force between the rubber conveyor belt and the surface of the base material of the refractory multilayer sheet in contact with the conveyor belt becomes large, and good transportability cannot be obtained. If it exceeds 50 μm, the frictional force becomes too low and problems such as difficulty in fixing the position are likely to occur. Ra is preferably 0.4 μm or more, and more preferably 0.5 μm or more. Further, it is preferably 10 μm or less, and more preferably 5 μm or less. The surface roughness Ra can be measured by the method described in Examples.
By reducing the surface roughness as in the above range, it becomes easier to apply the adhesive to the side of the first base material where the thermal expansion resin layer is not provided, and the refractory multilayer sheet has a good adhesive function. Can have.
Ｒａを０．２μｍ〜５０μｍとするには、熱膨張樹脂層が設けられない側の面にサンドブラスト処理やケミカルブラストを施せばよく、なかでもサンドブラスト処理が好ましい。サンドブラスト処理の方法としては、上記の面にショットブラスト機で研磨材を遠心力で投射する方法等が挙げられる。
また、天然樹脂、合成樹脂を第１の基材に使用する場合に、Ｒａが０．２μｍ〜５０μｍである不織布を熱膨張樹脂層が設けられない側の面に積層して第１の基材としてもよい。
In order to set Ra to 0.2 μm to 50 μm, sandblasting or chemical blasting may be performed on the surface on the side where the thermal expansion resin layer is not provided, and sandblasting is particularly preferable. Examples of the sandblasting method include a method of projecting an abrasive by centrifugal force onto the above surface with a shot blasting machine.
Further, when a natural resin or a synthetic resin is used as the first base material, a non-woven fabric having a Ra of 0.2 μm to 50 μm is laminated on the surface on the side where the thermal expansion resin layer is not provided, and the first base material is used. May be.
第１の基材としては、布材、天然樹脂、合成樹脂等が挙げられる。
布材としては、例えば、木綿、絹、ナイロン、ＰＥＴ等のポリエステル、ポリプロピレン等のポリオレフィン等の織布、不織布が挙げられる。これらは主に、天然樹脂又は合成樹脂と組み合わせて使用することが好ましい。すなわち、天然樹脂製の基材又は合成樹脂製の基材の熱膨張樹脂層が設けられない側の面に、Ｒａを０．２μｍ〜５０μｍとするための布材を積層して、第１の基材とすることが好ましい。
天然樹脂としては、例えば、セルロース誘導体、ゼラチン、アルギン酸塩、キトサン、プルラン、ペクチン、カラゲナン、タンパク質、タンニン、リグニン、ロジン酸等を主成分とする高分子、天然ゴム等が挙げられる。
合成樹脂としては、例えば、イソプレンゴム、ブタジエンゴム、１，２−ポリブタジエンゴム、スチレン−ブタジエンゴム、クロロプレンゴム、ニトリルゴム、ブチルゴム、エチレン−プロピレンゴム、クロロスルホン化ポリエチレン、アクリルゴム、エピクロルヒドリンゴム、シリコーンゴム、フッ素ゴム、ウレタンゴム、ポリイソブチレンゴム、塩化ブチルゴム等の合成ゴム、ポリプロピレン樹脂、ポリエチレン樹脂、ポリ（１−）ブテン樹脂、ポリペンテン樹脂等のポリオレフィン樹脂、ポリスチレン樹脂、アクリロニトリル−ブタジエン−スチレン樹脂、ポリカーボネート樹脂、アクリル樹脂、ポリアミド樹脂、ポリ塩化ビニル樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂のポリエステル樹脂、ポリフェニレンエーテル樹脂、全芳香族ポリエステル樹脂、ポリエーテルスルホン樹脂、フェノール樹脂、ポリウレタン樹脂、エポキシ樹脂等が挙げられ、ポリエチレン樹脂等のポリオレフィン樹脂、ポリエチレンテレフタレート樹脂（ＰＥＴ）、ポリブチレンテレフタレート樹脂等のポリエステル樹脂が好ましい。
Examples of the first base material include cloth materials, natural resins, synthetic resins and the like.
Examples of the cloth material include polyester such as cotton, silk, nylon and PET, woven cloth such as polyolefin such as polypropylene, and non-woven fabric. These are mainly preferably used in combination with natural resins or synthetic resins. That is, a cloth material for setting Ra of 0.2 μm to 50 μm is laminated on the surface of the base material made of natural resin or the base material made of synthetic resin on the side where the thermal expansion resin layer is not provided. It is preferably used as a base material.
Examples of the natural resin include cellulose derivatives, gelatin, alginate, chitosan, purulan, pectin, carrageenan, protein, tannin, lignin, a polymer containing rosinic acid as a main component, natural rubber and the like.
Examples of the synthetic resin include isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, and silicone. Synthetic rubber such as rubber, fluororubber, urethane rubber, polyisobutylene rubber, butyl chloride rubber, polypropylene resin, polyethylene resin, poly (1-) butene resin, polyolefin resin such as polypentene resin, polystyrene resin, acrylonitrile-butadiene-styrene resin, Polycarbonate resin, acrylic resin, polyamide resin, polyvinyl chloride resin, polyethylene terephthalate resin, polybutylene terephthalate resin polyester resin, polyphenylene ether resin, all aromatic polyester resin, polyether sulfone resin, phenol resin, polyurethane resin, epoxy resin, etc. However, polyolefin resins such as polyethylene resin, polyester resins such as polyethylene terephthalate resin (PET) and polybutylene terephthalate resin are preferable.
第１の基材は、異種若しくは同種の材料で２層以上としてもよい。２層以上とすることで、それぞれの素材を生かした基材することができる。例えば、第１の基材を、ポリエチレン基材又はＰＥＴ基材の熱膨張樹脂層が設けられない側の面に不織布を積層した不織布積層基材とすると、良好な搬送性を有しながら、不織布による破断防止等の効果が得られる。 The first base material may be made of different or similar materials and may have two or more layers. By using two or more layers, it is possible to make a base material that makes the best use of each material. For example, when the first base material is a non-woven fabric laminated base material in which a non-woven fabric is laminated on the surface of the polyethylene base material or the PET base material on the side where the thermal expansion resin layer is not provided, the non-woven fabric has good transportability. The effect of preventing breakage can be obtained.
第１の基材の厚み（多層の場合はその合計）は特に限定されないが、１０μｍ〜１ｍｍであることが好ましく、５０〜４００μｍがより好ましい。 The thickness of the first base material (in the case of multiple layers, the total) is not particularly limited, but is preferably 10 μm to 1 mm, more preferably 50 to 400 μm.
（第２の基材）
第２の基材は、粉体塗装等の塗装が施される。したがって第２の基材としては、第１基材と同様であるが、なかでも白色であることが好ましい。ここで、「白色」とは完全に白色であることに限られず、黄白色、赤白色、黒白色（灰色）、緑白色、青白色、茶白色、金白色、銀白色等、白色以外の各色であって白色度が高いものを含む。本明細書において、白色度が十分であるとはＪＩＳＺ８７１５（色の表示方法−白色度）の白色度指数が８０以上であるものをいう。
(Second base material)
The second base material is coated with powder coating or the like. Therefore, the second base material is the same as that of the first base material, but is preferably white. Here, "white" is not limited to completely white, and each color other than white, such as yellowish white, reddish white, blackish white (gray), greenish white, bluish white, brownish white, golden white, and silvery white, is used. Including those with high whiteness. In the present specification, sufficient whiteness means that the whiteness index of JISZ8715 (color display method-whiteness) is 80 or more.
第２の基材を白色とするには公知の方法を適用できる。例えば、酸化チタン、酸化亜鉛、硫化亜鉛、リトポン、炭酸カルシウム、シリカ、カオリン、クレイ等の無機材と既述の樹脂からなるペレットを押出機に供給し、２８０℃程度の温度で溶融押し出し、３０μｍカットフィルター等により濾過を行い、Ｔダイ口金に導入しシート状に押出成形することで白色の第２の基材が得られる。 A known method can be applied to make the second substrate white. For example, pellets made of an inorganic material such as titanium oxide, zinc oxide, zinc sulfide, lithopone, calcium carbonate, silica, kaolin, clay and the above-mentioned resin are supplied to an extruder and melt-extruded at a temperature of about 280 ° C. to 30 μm. A white second base material can be obtained by filtering with a cut filter or the like, introducing it into a T-die base, and extruding it into a sheet.
第２の基材における熱膨張樹脂層が設けられていない側の面の表面粗さＲａは、１．５μｍ以下であることが好ましく、０．５μｍ以下であることがより好ましい。特にＲａが０．５μｍ以下であることで、適度なツヤが得られて美観が増し、粉体塗装がしやすいといった効果が得られる。Ｒａは、０．３μｍ以下であることがさらに好ましく、０．１μｍ以下であることがよりさらに好ましい。また、実際的には、Ｒａは０．０３μｍ以上となる。 The surface roughness Ra of the surface of the second base material on the side where the thermal expansion resin layer is not provided is preferably 1.5 μm or less, and more preferably 0.5 μm or less. In particular, when Ra is 0.5 μm or less, an appropriate gloss is obtained, the aesthetic appearance is increased, and the effect of easy powder coating can be obtained. Ra is further preferably 0.3 μm or less, and even more preferably 0.1 μm or less. Further, in practice, Ra is 0.03 μm or more.
第２の基材は、第１の基材と同様に、異種若しくは同種の材料で２層以上としてもよい。また、第２の基材の厚み（多層の場合はその合計）は特に限定されないが、３０μｍ〜０．４ｍｍであることが好ましく、５０〜２００μｍがより好ましい。 Like the first base material, the second base material may be made of different or similar materials and may have two or more layers. The thickness of the second base material (the total thickness in the case of multiple layers) is not particularly limited, but is preferably 30 μm to 0.4 mm, more preferably 50 to 200 μm.
本発明において、第１の基材及び第２の基材の軟化点はそれぞれ２００℃以上であることが好ましい。２００℃以上であることで、粉体塗装等の塗装で焼き付け処理等が施されても良好な形態保持性が得られる。軟化点は、ＪＩＳ Ｋ ２２０７に準拠して測定した値とする。基材が多層の場合は、軟化点の低い方の値が２００℃以上であることが好ましい。 In the present invention, the softening points of the first base material and the second base material are preferably 200 ° C. or higher, respectively. When the temperature is 200 ° C. or higher, good morphological retention can be obtained even if a baking treatment or the like is performed by coating such as powder coating. The softening point shall be a value measured in accordance with JIS K 2207. When the base material has multiple layers, the value having the lower softening point is preferably 200 ° C. or higher.
（熱膨張樹脂層）
熱膨張樹脂層は、樹脂と熱膨張性黒鉛とを含む。具体的には樹脂と熱膨張性黒鉛とを含む熱膨張性樹脂組成物から構成される。
(Thermal expansion resin layer)
The heat-expandable resin layer contains a resin and heat-expandable graphite. Specifically, it is composed of a heat-expandable resin composition containing a resin and heat-expandable graphite.
（１）樹脂
樹脂としては、公知の樹脂を広く使用でき、例えば、熱硬化性樹脂、熱可塑性樹脂、及びエラストマー樹脂が挙げられる。これらの樹脂は、１種を単独で用いても、２種以上を混合して用いてもよい。
(1) Resin As the resin, known resins can be widely used, and examples thereof include thermosetting resins, thermoplastic resins, and elastomer resins. These resins may be used alone or in combination of two or more.
熱硬化性樹脂としては、例えば、ポリウレタン、ポリイソシアネート、ポリイソシアヌレート、フェノール樹脂、エポキシ樹脂、尿素樹脂、メラミン樹脂、不飽和ポリエステル樹脂、ポリイミド等の合成樹脂が挙げられ、エポキシ樹脂が好ましい。 Examples of the thermosetting resin include synthetic resins such as polyurethane, polyisocyanate, polyisocyanurate, phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, and polyimide, and epoxy resin is preferable.
ここで、エポキシ樹脂は、特に限定されないが、基本的にはエポキシ基をもつモノマーと硬化剤を反応させることにより得られる。上記エポキシ基をもつモノマーとしては、２官能のグリシジルエーテル型、グリシジルエステル型、多官能のグリシジルエーテル型等のものが挙げられる。
硬化剤は、重付加型、触媒型のものが挙げられる。重付加型の硬化剤としては、例えば、ポリアミン、酸無水物、ポリフェノール、ポリメルカプタン等が例示される。また、上記触媒型の硬化剤としては、例えば、３級アミン、イミダゾール類、ルイス酸錯体等が例示される。
Here, the epoxy resin is not particularly limited, but is basically obtained by reacting a monomer having an epoxy group with a curing agent. Examples of the monomer having an epoxy group include bifunctional glycidyl ether type, glycidyl ester type, and polyfunctional glycidyl ether type.
Examples of the curing agent include a heavy addition type and a catalytic type. Examples of the heavy addition type curing agent include polyamines, acid anhydrides, polyphenols, and polymercaptans. Examples of the catalyst-type curing agent include tertiary amines, imidazoles, and Lewis acid complexes.
熱可塑性樹脂としては、例えば、ポリプロピレン樹脂、ポリエチレン樹脂、ポリ（１−）ブテン樹脂、及びポリペンテン樹脂等のポリオレフィン樹脂、ポリエチレンテレフタレート等のポリエステル樹脂、ポリスチレン樹脂、アクリロニトリル−ブタジエン−スチレン（ＡＢＳ）樹脂、エチレンビニルアセテート樹脂（ＥＶＡ）、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、（メタ）アクリル系樹脂、ポリアミド樹脂、ポリ塩化ビニル樹脂（ＰＶＣ）、ノボラック樹脂、ポリウレタン樹脂、及びポリイソブチレン等の合成樹脂が挙げられる。なかでも、エチレンビニルアセテート樹脂が好ましい。 Examples of the thermoplastic resin include polypropylene resins, polyethylene resins, poly (1-) butene resins, polyolefin resins such as polypentene resins, polyester resins such as polyethylene terephthalate, polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, and the like. Examples thereof include synthetic resins such as ethylene vinyl acetate resin (EVA), polycarbonate resin, polyphenylene ether resin, (meth) acrylic resin, polyamide resin, polyvinyl chloride resin (PVC), novolak resin, polyurethane resin, and polyisobutylene. Of these, ethylene vinyl acetate resin is preferable.
エラストマー樹脂としては、クロロプレンゴム、アクリロニトリルブタジエンゴム、液状アクリロニトリルブタジエンゴム、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）、液状エチレン−プロピレン−ジエンゴム（液状ＥＰＤＭ）、エチレン−プロピレンゴム、液状エチレン−プロピレンゴム、天然ゴム、液状天然ゴム、ポリブタジエンゴム、液状ポリブタジエンゴム、ポリイソプレンゴム、液状ポリイソプレンゴム、スチレン−ブタジエンブロック共重合体、液状スチレン−ブタジエンブロック共重合体、水素添加スチレン−ブタジエンブロック共重合体、液状水素添加スチレン−ブタジエンブロック共重合体、水素添加スチレン−ブタジエン−スチレンブロック共重合体、液状水素添加スチレン−ブタジエン−スチレンブロック共重合体、水素添加スチレン−イソプレンブロック共重合体、液状水素添加スチレン−イソプレンブロック共重合体、水素添加スチレン−イソプレン−スチレンブロック共重合体、及び液状水素添加スチレン−イソプレン−スチレンブロック共重合体等が挙げられる。なかでも、クロロプレンゴムが好ましい。 Elastol resins include chloroprene rubber, acrylonitrile butadiene rubber, liquid acrylonitrile butadiene rubber, ethylene-propylene-diene rubber (EPDM), liquid ethylene-propylene-diene rubber (liquid EPDM), ethylene-propylene rubber, liquid ethylene-propylene rubber, and natural rubber. , Liquid natural rubber, polybutadiene rubber, liquid polybutadiene rubber, polyisoprene rubber, liquid polyisoprene rubber, styrene-butadiene block copolymer, liquid styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, liquid hydrogen Additive styrene-butadiene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, liquid hydrogenated styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene block copolymer, liquid hydrogenated styrene-isoprene Examples thereof include block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, and liquid hydrogenated styrene-isoprene-styrene block copolymers. Of these, chloroprene rubber is preferable.
本発明においては、加熱時の熱収縮率が少なく、効果的に防火性能を向上させる観点から、熱硬化性樹脂を含むことが好ましく、樹脂自体の難燃性を上げて防火性能を向上させるという観点からは、エポキシ樹脂を含むことがより好ましい。 In the present invention, it is preferable to contain a thermosetting resin from the viewpoint that the heat shrinkage rate at the time of heating is small and the fireproof performance is effectively improved, and the flame retardancy of the resin itself is increased to improve the fireproof performance. From the viewpoint, it is more preferable to contain an epoxy resin.
熱膨張性樹脂組成物中の樹脂の含有量は、好ましくは５質量％以上、より好ましくは６質量％以上、さらに好ましくは８質量％以上である。熱膨張性樹脂組成物中の樹脂の含有量をこれら下限値以上とすると、熱膨張樹脂層とする際の成形性が向上する。また、上記含有量は、好ましくは８５質量％以下、より好ましくは８０質量％以下、さらに好ましくは５０質量％以下、よりさらに好ましくは１５質量％以下である。 The content of the resin in the heat-expandable resin composition is preferably 5% by mass or more, more preferably 6% by mass or more, and further preferably 8% by mass or more. When the content of the resin in the heat-expandable resin composition is at least these lower limit values, the moldability when forming the heat-expandable resin layer is improved. The content is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 50% by mass or less, still more preferably 15% by mass or less.
（２）熱膨張性黒鉛
熱膨張性黒鉛は加熱されることで膨張して大容量の空隙を形成し、難燃剤として機能する。その結果、耐火多層シートに着火した場合に延焼を抑制することができる。
(2) Thermally expandable graphite Thermally expandable graphite expands when heated to form large-capacity voids and functions as a flame retardant. As a result, it is possible to suppress the spread of fire when the refractory multilayer sheet is ignited.
熱膨張性黒鉛としては、加熱時に膨張する黒鉛であれば特に制限はなく、天然鱗状グラファイト、熱分解グラファイト、及びキッシュグラファイト等の粉末を無機酸と強酸化剤とで処理してグラファイト層間化合物を生成させたものが挙げられ、これらは炭素の層状構造を維持したままの結晶化合物になっている。
無機酸としては濃硫酸、硝酸、及びセレン酸等が挙げられ、強酸化剤としては濃硝酸、過塩素酸、過塩素酸塩、過マンガン酸塩、重クロム酸塩、及び過酸化水素等が挙げられる。
熱膨張性黒鉛は更に中和処理を行ったものでもよい。具体的には、酸処理により得られた熱膨張性黒鉛を、更にアンモニア、脂肪族低級アミン、アルカリ金属化合物、アルカリ土類金属化合物等で中和することが好ましい。
熱膨張性黒鉛の粒度は、２０〜２００メッシュが好ましい。膨張性黒鉛の粒度が上記範囲内であると、膨脹して大容量の空隙を作りやすくなるため難燃性が向上する。また、樹脂への分散性も向上する。
The heat-expandable graphite is not particularly limited as long as it expands when heated, and powders such as natural scaly graphite, pyrolytic graphite, and kiss graphite are treated with an inorganic acid and a strong oxidizing agent to form a graphite intercalation compound. Examples include those produced, which are crystalline compounds that maintain the layered structure of carbon.
Examples of the inorganic acid include concentrated sulfuric acid, nitric acid, and selenic acid, and examples of the strong oxidizing agent include concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, and hydrogen peroxide. Can be mentioned.
The heat-expandable graphite may be further neutralized. Specifically, it is preferable to further neutralize the heat-expandable graphite obtained by the acid treatment with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound or the like.
The particle size of the heat-expandable graphite is preferably 20 to 200 mesh. When the particle size of the expandable graphite is within the above range, it expands and easily forms a large-capacity void, so that the flame retardancy is improved. In addition, the dispersibility in the resin is also improved.
熱膨張性黒鉛の平均アスペクト比は、２以上が好ましく、５以上がより好ましく、１０以上が更に好ましい。熱膨張性黒鉛の平均アスペクト比の上限は特に限定されないが、熱膨張性黒鉛の割れ防止の観点から、１，０００以下であることが好ましい。熱膨張性黒鉛の平均アスペクト比が２以上であることにより、膨張して大容量の空隙を作りやすくなるため難燃性が向上する。
熱膨張性黒鉛の平均アスペクト比は、１０個の熱膨張性黒鉛について、それぞれ最大寸法（長径）及び最小寸法（短径）を測定し、最大寸法（長径）を最小寸法（短径）で除した値の平均値を平均アスペクト比とする。熱膨張性黒鉛の長径及び短径は、例えば、電界放出型走査電子顕微鏡（ＦＥ−ＳＥＭ）を用いて測定することができる。
The average aspect ratio of the heat-expandable graphite is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. The upper limit of the average aspect ratio of the heat-expandable graphite is not particularly limited, but is preferably 1,000 or less from the viewpoint of preventing cracking of the heat-expandable graphite. When the average aspect ratio of the heat-expandable graphite is 2 or more, it expands and easily forms a large-capacity void, so that flame retardancy is improved.
The average aspect ratio of the heat-expandable graphite is such that the maximum dimension (major axis) and the minimum dimension (minor axis) are measured for each of the 10 thermally expandable graphites, and the maximum dimension (major axis) is divided by the minimum dimension (minor axis). Let the average value of these values be the average aspect ratio. The major axis and minor axis of the heat-expandable graphite can be measured using, for example, a field emission scanning electron microscope (FE-SEM).
熱膨張性樹脂組成物中の熱膨張性黒鉛の含有量は樹脂１００質量部に対して、１０〜２００質量部が好ましく、２０〜１５０質量部がより好ましく、３０〜１００質量部が更に好ましい。熱膨張性黒鉛の含有量が前記範囲内であると、熱膨張性樹脂組成物中に大容量の空隙を作りやすくなるため難燃性が向上する。 The content of the heat-expandable graphite in the heat-expandable resin composition is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, and further preferably 30 to 100 parts by mass with respect to 100 parts by mass of the resin. When the content of the heat-expandable graphite is within the above range, a large-capacity void is easily formed in the heat-expandable resin composition, so that the flame retardancy is improved.
（３）難燃剤
熱膨張性樹脂組成物は、防火性能を向上させるために、熱膨張性黒鉛以外の難燃剤をさらに含有してもよい。難燃剤としては、例えば、赤リン、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、及びキシレニルジフェニルホスフェート等の各種リン酸エステル、リン酸ナトリウム、リン酸カリウム、及びリン酸マグネシウム等のリン酸金属塩、ポリリン酸アンモニウム、下記一般式（１）で表される化合物等が挙げられる。
(3) Flame Retardant The heat-expandable resin composition may further contain a flame retardant other than the heat-expandable graphite in order to improve the fire protection performance. Examples of the flame retardant include various phosphate esters such as red phosphorus, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresil diphenyl phosphate, and xylenyl diphenyl phosphate, sodium phosphate, potassium phosphate, and the like. Examples thereof include metal phosphates such as magnesium phosphate, ammonium polyphosphate, and compounds represented by the following general formula (1).
一般式（１）中、Ｒ１及びＲ３は、同一又は異なって、水素、炭素数１〜１６の直鎖状もしくは分岐状のアルキル基、又は炭素数６〜１６のアリール基を示す。Ｒ２は、水酸基、炭素数１〜１６の直鎖状もしくは分岐状のアルキル基、炭素数１〜１６の直鎖状もしくは分岐状のアルコキシル基、炭素数６〜１６のアリール基、又は炭素数６〜１６のアリールオキシ基を示す。 In the general formula (1), R 1 and R 3 represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms, which are the same or different. R 2 is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or a carbon number of carbon atoms. It shows 6 to 16 aryloxy groups.
一般式（１）で表される化合物の具体例としては、メチルホスホン酸、メチルホスホン酸ジメチル、メチルホスホン酸ジエチル、エチルホスホン酸、ｎ−プロピルホスホン酸、ｎ−ブチルホスホン酸、２−メチルプロピルホスホン酸、ｔ−ブチルホスホン酸、２，３−ジメチル−ブチルホスホン酸、オクチルホスホン酸、フェニルホスホン酸、ジオクチルフェニルホスホネート、ジメチルホスフィン酸、メチルエチルホスフィン酸、メチルプロピルホスフィン酸、ジエチルホスフィン酸、ジオクチルホスフィン酸、フェニルホスフィン酸、ジエチルフェニルホスフィン酸、ジフェニルホスフィン酸、ビス（４−メトキシフェニル）ホスフィン酸等が挙げられる。難燃剤は、単独でも、２種以上を組み合わせて用いてもよい。
難燃剤の中でも、耐火シートの難燃性を向上させる観点から、赤リン、ポリリン酸アンモニウム、及び前記一般式（１）で表される化合物が好ましく、難燃性能、安全性、及びコスト等の観点からポリリン酸アンモニウムがより好ましい。
Specific examples of the compound represented by the general formula (1) include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, n-propylphosphonic acid, n-butylphosphonic acid, 2-methylpropylphosphonic acid, and the like. t-Butylphosphonic acid, 2,3-dimethyl-butylphosphonate, octylphosphonate, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphonate, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphonic acid, dioctylphosphonate Examples thereof include phenylphosphonic acid, diethylphenylphosphonic acid, diphenylphosphonic acid, and bis (4-methoxyphenyl) phosphonic acid. The flame retardant may be used alone or in combination of two or more.
Among the flame retardants, red phosphorus, ammonium polyphosphate, and the compound represented by the general formula (1) are preferable from the viewpoint of improving the flame retardancy of the fireproof sheet, and the flame retardant performance, safety, cost, etc. From the viewpoint, ammonium polyphosphate is more preferable.
本発明の耐火樹脂組成物が難燃剤を含有する場合、その含有量は樹脂１００質量部に対して、１〜３００質量部が好ましく、５〜２００質量部がより好ましい。難燃剤の含有量が上記範囲内であると、耐火多層シートが着火した場合に延焼を抑制することができる。 When the refractory resin composition of the present invention contains a flame retardant, the content thereof is preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass with respect to 100 parts by mass of the resin. When the content of the flame retardant is within the above range, it is possible to suppress the spread of fire when the refractory multilayer sheet ignites.
（４）無機充填剤
熱膨張性樹脂組成物は、熱膨張性黒鉛及び難燃剤以外の無機充填剤をさらに含有してもよい。
無機充填剤は、膨張断熱層が形成される際、熱容量を増大させ伝熱を抑制するとともに、骨材的に働いて膨張断熱層の強度を向上させる。無機充填剤としては特に限定されず、例えば、アルミナ、酸化亜鉛、酸化チタン、酸化カルシウム、酸化マグネシウム、酸化鉄、酸化錫、酸化アンチモン、フェライト等の金属酸化物；水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、ハイドロタルサイト等の含水無機物；塩基性炭酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、炭酸ストロンチウム、炭酸バリウム等の金属炭酸塩等が挙げられる。なかでも、炭酸カルシウムが好ましい。
(4) Inorganic Filler The heat-expandable resin composition may further contain an inorganic filler other than the heat-expandable graphite and the flame retardant.
When the expanded heat insulating layer is formed, the inorganic filler increases the heat capacity and suppresses heat transfer, and also acts as an aggregate to improve the strength of the expanded heat insulating layer. The inorganic filler is not particularly limited, and for example, metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrite; calcium hydroxide, magnesium hydroxide, etc. Hydrous inorganic substances such as aluminum hydroxide and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate and barium carbonate can be mentioned. Of these, calcium carbonate is preferable.
また、無機充填剤としては、これらの他に、硫酸カルシウム、石膏繊維、ケイ酸カルシウム等のカルシウム塩；シリカ、珪藻土、ドーソナイト、硫酸バリウム、タルク、クレー、マイカ、モンモリロナイト、ベントナイト、活性白土、セピオライト、イモゴライト、セリサイト、ガラス繊維、ガラスビーズ、シリカ系バルン、窒化アルミニウム、窒化ホウ素、窒化ケイ素、カーボンブラック、グラファイト、炭素繊維、炭素バルン、木炭粉末、各種金属粉、チタン酸カリウム、硫酸マグネシウム、チタン酸ジルコン酸鉛、ステアリン酸亜鉛、ステアリン酸カルシウム、アルミニウムボレート、硫化モリブデン、炭化ケイ素、ステンレス繊維、ホウ酸亜鉛、各種磁性粉、スラグ繊維、フライアッシュ、脱水汚泥等が挙げられる。これらの無機充填剤は単独で用いることができるし、２種以上を併用することもできる。 In addition to these, other inorganic fillers include calcium salts such as calcium sulfate, gypsum fiber, and calcium silicate; silica, diatomaceous earth, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, and sepiolite. , Imogolite, sericite, glass fiber, glass beads, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, Examples thereof include lead zirconate titanate, zinc stearate, calcium stearate, aluminum borate, molybdenum sulfide, silicon carbide, stainless fiber, zinc borate, various magnetic powders, slag fiber, fly ash, and dehydrated sludge. These inorganic fillers can be used alone or in combination of two or more.
無機充填剤の平均粒子径としては、０．５〜１００μｍが好ましく、より好ましくは１〜５０μｍである。無機充填剤は、添加量が少ないときは、分散性が性能を大きく左右するため、粒径の小さいものが好ましいが、０．５μｍ以上であると、分散性が良好である。添加量が多いときは、高充填が進むにつれて、熱膨張性樹脂組成物の粘度が高くなり成形性が低下するが、粒径を大きくすることで熱膨張性樹脂組成物の粘度を低下させることができる点から、平均粒子径の大きいものが好ましいが、１００μｍ以下の平均粒子径が熱膨張樹脂層の力学的物性の点で望ましい。
なお、本明細書において平均粒子径は、レーザー回折／散乱式粒度分布測定装置により測定したメディアン径（Ｄ５０）の値である。
The average particle size of the inorganic filler is preferably 0.5 to 100 μm, more preferably 1 to 50 μm. When the amount of the inorganic filler added is small, the dispersibility greatly affects the performance, so that the inorganic filler has a small particle size, but when it is 0.5 μm or more, the dispersibility is good. When the amount added is large, the viscosity of the heat-expandable resin composition increases and the moldability decreases as the high filling progresses, but the viscosity of the heat-expandable resin composition decreases by increasing the particle size. It is preferable that the average particle size is large, but the average particle size of 100 μm or less is preferable from the viewpoint of the mechanical properties of the thermal expansion resin layer.
In the present specification, the average particle size is a value of the median diameter (D50) measured by a laser diffraction / scattering type particle size distribution measuring device.
無機充填剤の含有量は樹脂１００質量部に対して、好ましくは１０〜３００質量部、より好ましくは１０〜２００質量部である。無機充填剤の含有量が前記範囲内であると、これを用いた熱膨張樹脂層の機械的物性を向上させることができる。 The content of the inorganic filler is preferably 10 to 300 parts by mass, more preferably 10 to 200 parts by mass with respect to 100 parts by mass of the resin. When the content of the inorganic filler is within the above range, the mechanical properties of the heat-expandable resin layer using the inorganic filler can be improved.
（５）可塑剤
熱膨張性樹脂組成物は可塑剤をさらに含有してもよい。
可塑剤は、一般にポリ塩化ビニル樹脂成形体を製造する際に使用されている可塑剤であれば特に限定されない。具体的には、例えば、ジ−２−エチルヘキシルフタレート（ＤＯＰ）、ジブチルフタレート（ＤＢＰ）、ジヘプチルフタレート（ＤＨＰ）、ジイソデシルフタレート（ＤＩＤＰ）等のフタル酸エステル可塑剤、ジ−２−エチルヘキシルアジペート（ＤＯＡ）、ジイソブチルアジペート（ＤＩＢＡ）、ジブチルアジペート（ＤＢＡ）等の脂肪酸エステル可塑剤、エポキシ化大豆油等のエポキシ化エステル可塑剤、アジピン酸エステル、アジピン酸ポリエステル等のアジピン酸エステル可塑剤、トリー２−エチルヘキシルトリメリテート（ＴＯＴＭ）、トリイソノニルトリメリテート（ＴＩＮＴＭ）等のトリメリット酸エステル可塑剤、鉱油等のプロセスオイル等が挙げられる。可塑剤は、１種単独で用いても、２種以上を組み合わせて用いてもよい。
熱膨張性樹脂組成物が可塑剤を含有する場合、その含有量は、樹脂１００質量部に対して５〜４０質量部が好ましく、５〜３５質量部がより好ましい。可塑剤の含有量が上位範囲内であると、押出成形性が向上する傾向があり、また成形体が柔らかくなり過ぎることを抑制することができる。
(5) Plasticizer The heat-expandable resin composition may further contain a plasticizer.
The plasticizer is not particularly limited as long as it is a plasticizer generally used in producing a polyvinyl chloride resin molded product. Specifically, for example, phthalate ester plasticizers such as di-2-ethylhexylphthalate (DOP), dibutylphthalate (DBP), diheptylphthalate (DHP), and diisodecylphthalate (DIDP), di-2-ethylhexyl adipate (di-2-ethylhexyl adipate). DOA), diisobutyl adipate (DIBA), dibutyl adipate (DBA) and other fatty acid ester plasticizers, epoxidized soybean oil and other epoxidized ester plasticizers, adipic acid ester, adipate polyester and other adipic acid ester plasticizers, Tory 2 -Examples include trimellitic acid ester plasticizers such as ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM), and process oils such as mineral oil. The plasticizer may be used alone or in combination of two or more.
When the heat-expandable resin composition contains a plasticizer, the content thereof is preferably 5 to 40 parts by mass, more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the resin. When the content of the plasticizer is in the upper range, the extrusion moldability tends to be improved, and it is possible to prevent the molded product from becoming too soft.
さらに熱膨張性樹脂組成物は、それぞれ本発明の目的を損なわない範囲で、必要に応じて、フェノール系、アミン系、イオウ系等の酸化防止剤の他、金属害防止剤、帯電防止剤、安定剤、架橋剤、滑剤、軟化剤、顔料、粘着付与樹脂、成型補助材等の添加剤、ポリブテン、石油樹脂等の粘着付与剤を含むことができる。 Further, the heat-expandable resin composition includes, as necessary, phenol-based, amine-based, sulfur-based antioxidants, metal damage inhibitors, antistatic agents, and the like, as long as the object of the present invention is not impaired. Additives such as stabilizers, cross-linking agents, lubricants, softeners, pigments, antistatic resins, molding aids, and antistatic agents such as polybutene and petroleum resins can be included.
熱膨張樹脂層の厚みは、取り扱い性の観点から、０．５〜２．５ｍｍが好ましく、１．０〜２．０ｍｍがより好ましい。 The thickness of the heat-expandable resin layer is preferably 0.5 to 2.5 mm, more preferably 1.0 to 2.0 mm from the viewpoint of handleability.
耐火多層シートの厚みは特に限定はないが、０．１〜３ｍｍが好ましく、０．３〜２ｍｍがより好ましい。なお、本明細書における耐火多層シートの「厚み」とは、耐火多層シートの幅方向３点の平均厚みを指す。
また、耐火多層シートは、第１の基材における熱膨張樹脂層が設けられていない側の面に粘着剤及びセパレータの少なくともいずれかを備えることが好ましい。
粘着剤としては、特に制限はなく、例えば、アクリル系粘着剤、ウレタン系粘着剤、ゴム系粘着剤等が挙げられるが、これらに限定されない。粘着剤からなる粘着剤層の厚みは、特に限定されないが、例えば、３〜５００μｍ、好ましくは１０〜２００μｍである。
また、セパレータとしては、ポリ塩化ビニル、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル、ポリエチレン、ポリプロピレン、ポリ（１−ブテン）、ポリペンテン等のポリオレフィン、ポリ酢酸ビニル、ポリスチレン、アクリル樹脂、アクリロニトリル−ブタジエン−スチレン（ＡＢＳ）樹脂、ポリカーボネート、ポリアミド、ポリフェニレンエーテル、ポリエーテルスルホン、紙等のようなものが挙げられ、その厚みは、例えば、２０〜２００μｍ、好ましくは５０〜１００μｍである。セパレータは、上記粘着剤を介して、又は、直接第１の基材に設けられていてもよい。
The thickness of the refractory multilayer sheet is not particularly limited, but is preferably 0.1 to 3 mm, more preferably 0.3 to 2 mm. The "thickness" of the refractory multilayer sheet in the present specification refers to the average thickness of three points in the width direction of the refractory multilayer sheet.
Further, the refractory multilayer sheet preferably has at least one of an adhesive and a separator on the surface of the first base material on the side where the thermal expansion resin layer is not provided.
The pressure-sensitive adhesive is not particularly limited, and examples thereof include, but are not limited to, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a rubber-based pressure-sensitive adhesive. The thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive is not particularly limited, but is, for example, 3 to 500 μm, preferably 10 to 200 μm.
The separators include polyesters such as polyvinyl chloride, polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polyethylene, polypropylene, poly (1-butene) and polypentene, polyvinyl acetate, polystyrene, acrylic resin and acrylonitrile-butadiene-styrene. Examples thereof include (ABS) resin, polycarbonate, polyamide, polyphenylene ether, polyether sulfone, paper and the like, and the thickness thereof is, for example, 20 to 200 μm, preferably 50 to 100 μm. The separator may be provided on the first substrate via the above-mentioned adhesive or directly.
＜耐火多層シートの製造方法＞
本発明の耐火多層シートは、第１の基材と熱膨張樹脂層と第２の基材とをこの順に積層し、この積層体をプレス処理等して、必要に応じて硬化炉にて加熱硬化させて製造することができる。
<Manufacturing method of refractory multilayer sheet>
In the refractory multilayer sheet of the present invention, the first base material, the heat-expandable resin layer, and the second base material are laminated in this order, the laminated body is pressed, and the like, and heated in a curing furnace as necessary. It can be cured and manufactured.
ここで上記積層体は、例えば図２に示すようにして作製することができる。まず、コンベア２０により搬送される第１の基材１２上に熱膨張樹脂層となる熱膨張性樹脂組成物１４Ａを容器２２から供給して塗膜を形成する。その後、熱膨張性樹脂組成物１４Ａの塗膜上にロール２４から繰り出される第２の基材１６が塗膜上に積層されて、積層体が得られる。
なお、熱膨張性樹脂組成物の種類によっては押出成型により第１の基材１２上に熱膨張樹脂組成物の成型物を付与し、ロール２４から繰り出される第２の基材１６をさらに積層する等して積層体としてもよい。
この一連のプロセスでコンベア２０のコンベアベルト表面と、これに接する第１の基材１２との摩擦が大きいと滑りがなくなりうまく搬送できなくなる。しかし、本発明の耐火多層シートの第１の基材１０は、ベルトとの接触面の表面粗さが所定の範囲とされているため、摩擦力が低減し良好な搬送性が得られ、耐火多層シートとされた後も摩擦力が低減し良好な搬送性が得られる。
Here, the laminate can be produced, for example, as shown in FIG. First, the heat-expandable resin composition 14A to be the heat-expandable resin layer is supplied from the container 22 onto the first base material 12 conveyed by the conveyor 20 to form a coating film. Then, the second base material 16 unwound from the roll 24 is laminated on the coating film of the heat-expandable resin composition 14A to obtain a laminated body.
Depending on the type of the heat-expandable resin composition, a molded product of the heat-expandable resin composition is applied onto the first base material 12 by extrusion molding, and the second base material 16 unwound from the roll 24 is further laminated. It may be made into a laminated body by equalizing.
In this series of processes, if the friction between the surface of the conveyor belt of the conveyor 20 and the first base material 12 in contact with the surface of the conveyor belt is large, slippage will not occur and the conveyor belt cannot be conveyed well. However, in the first base material 10 of the refractory multilayer sheet of the present invention, since the surface roughness of the contact surface with the belt is within a predetermined range, the frictional force is reduced and good transportability is obtained, and the refractory is fire resistant. Even after the multi-layer sheet is formed, the frictional force is reduced and good transportability can be obtained.
以上のような耐火多層シートは、第２の基材上に粉体塗装などの塗装処理が施される。塗装処理の際には、耐火多層シートの第１の基材がゴム製ベルト表面に載置されて搬送されるが、既述のとおり、第１の基材は、ゴム製ベルトとの接触面の表面粗さが所定の範囲とされているため良好な搬送性が得られる。
塗装処理後は、被着体の寸法に合わせてカット等し、例えば、一戸建住宅、集合住宅、高層住宅、高層ビル、商業施設、公共施設等の各種の建築物、自動車、電車などの各種車両、船舶、航空機などに使用できる。これらの中では建築物に使用されることが好ましい。
The fireproof multilayer sheet as described above is subjected to a coating treatment such as powder coating on the second base material. During the painting process, the first base material of the refractory multilayer sheet is placed on the surface of the rubber belt and conveyed. As described above, the first base material is the contact surface with the rubber belt. Since the surface roughness of the above is within a predetermined range, good transportability can be obtained.
After the painting process, it is cut according to the dimensions of the adherend, for example, various buildings such as detached houses, apartment houses, high-rise houses, high-rise buildings, commercial facilities, public facilities, automobiles, trains, etc. It can be used for vehicles, ships, aircraft, etc. Of these, it is preferably used for buildings.
また、粉体塗装などの塗装処理が施された耐火多層シートは、上記建築物、車両、船舶、航空機などを構成する部材に取り付けられて使用される。より具体的には、壁、床、レンガ、屋根、板材、窓、障子、扉、ドア、戸、ふすま、欄間、配線、配管などに取り付けられるが、これらに限定されない。 Further, the refractory multilayer sheet that has been subjected to a coating treatment such as powder coating is used by being attached to a member constituting the above-mentioned building, vehicle, ship, aircraft or the like. More specifically, it can be attached to walls, floors, bricks, roofs, plates, windows, shoji screens, doors, doors, doors, bran, columns, wiring, pipes, etc., but is not limited thereto.
ここで、粉体塗装としては、流動浸漬法、静電法、溶射法、回転成形法などの塗装方法が挙げられる。粉体による塗膜が形成された後は、加熱炉に投入し粉体が完全に溶融し平滑な表面に仕上がるまで加熱し、その後冷却する。 Here, examples of the powder coating include coating methods such as a flow immersion method, an electrostatic method, a thermal spraying method, and a rotary molding method. After the coating film is formed by the powder, it is put into a heating furnace, heated until the powder is completely melted and a smooth surface is finished, and then cooled.
加熱温度（焼付温度）は、粉体塗料の種類に応じて選択される。一例として、加熱温度（焼付温度）は、例えば、９０℃以上２５０℃以下が好ましく、１００℃以上２２０℃以下がより好ましく、１２０℃以上２００℃以下が更に好ましい。なお、加熱時間（焼付時間）は、加熱温度（焼付温度）に応じて調節する。 The heating temperature (baking temperature) is selected according to the type of powder coating material. As an example, the heating temperature (baking temperature) is, for example, preferably 90 ° C. or higher and 250 ° C. or lower, more preferably 100 ° C. or higher and 220 ° C. or lower, and further preferably 120 ° C. or higher and 200 ° C. or lower. The heating time (baking time) is adjusted according to the heating temperature (baking temperature).
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はこれらに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
＜実施例１＞
（第１の基材）
厚さ０．０１ｍｍのＰＥＴフィルム（帝人デュポンフィルム（株）社製、商品名：メリネックス）に５０ｇ／ｍ２の不織布（ＰＥＴ繊維）を２６０℃の条件でドライラミネートした、不織布積層基材（第１の基材、厚み０．２５ｍｍ）を用意した。
<Example 1>
(First base material)
A non-woven fabric laminated base material (No. 1) obtained by dry-laminating a 50 g / m 2 non-woven fabric (PET fiber) on a 0.01 mm thick PET film (manufactured by Teijin DuPont Film Co., Ltd., trade name: Melinex) under the condition of 260 ° C. 1 substrate, thickness 0.25 mm) was prepared.
表面粗さＲａは、キーエンス社製の形状測定マイクロスコープＶＫ−Ｘ１００を用いて、５倍の倍率で表面を観察した際の表面粗さ解析を行い測定した。 The surface roughness Ra was measured by performing a surface roughness analysis when observing the surface at a magnification of 5 times using a shape measuring microscope VK-X100 manufactured by KEYENCE CORPORATION.
（第２の基材）
厚さ０．１ｍｍの白色ＰＥＴフィルム（東レ（株）社製、商品名：ルミラーＥ２０）を用意し、これを第２の基材とした。なお、白色度は、９３であり、Ｒａは０．０８μｍであった。
(Second base material)
A white PET film with a thickness of 0.1 mm (manufactured by Toray Industries, Inc., trade name: Lumirror E20) was prepared and used as a second base material. The whiteness was 93 and Ra was 0.08 μm.
（熱膨張性樹脂組成物）
エポキシ樹脂：Ｅ８０７（三菱化学社製） ６０質量部
ジアミン系硬化剤：ＥＫＦＬ０５２（三菱化学社製）４０質量部
熱膨張性黒鉛：ＣＡ６０Ｎ（エアウォーター社製）１００質量部
ポリリン酸アンモニウム：ＡＰ４２２（クラリアントケミカルズ社製）１００質量部
炭酸カルシウム：ＢＦ３００（白石カルシウム社製）１００質量部
(Thermal expandable resin composition)
Epoxy resin: E807 (manufactured by Mitsubishi Chemical Corporation) 60 parts by mass Diamine-based curing agent: EKFL052 (manufactured by Mitsubishi Chemical Corporation) 40 parts by mass Heat-expandable graphite: CA60N (manufactured by Airwater) 100 parts by mass Ammonium polyphosphate: AP422 (clariant) Chemicals) 100 parts by mass Calcium carbonate: BF300 (manufactured by Shiraishi Calcium) 100 parts by mass
（耐火多層シートの作製）
第１の基材のＰＥＴフィルム面に熱膨張性樹脂組成物を塗布し、その後、第２の基材を積層し、プレス処理を施し、硬化炉にて９０℃で１５時間、加熱硬化させて耐火多層シート（厚さ：１．８ｍｍ）を作製した。
(Making a refractory multilayer sheet)
The heat-expandable resin composition is applied to the PET film surface of the first base material, then the second base material is laminated, pressed, and heat-cured at 90 ° C. for 15 hours in a curing furnace. A fireproof multilayer sheet (thickness: 1.8 mm) was prepared.
＜実施例２＞
厚さ０．１ｍｍのＰＥＴフィルム（帝人デュポンフィルム（株）社製、商品名：メリネックス）の片面にサンドブラスト処理を行って、表面粗さＲａを０．５μｍとした第１の基材を得た。その後、得られた第１の基材を用いた以外は実施例１と同様にして耐火多層シートを作製した。
なお、実施例におけるブラスト処理は、粒子径８０〜２００μｍのアルミナ粒子を基材に投射処理して行った。
<Example 2>
One side of a PET film having a thickness of 0.1 mm (manufactured by Teijin DuPont Film Co., Ltd., trade name: Melinex) was sandblasted to obtain a first substrate having a surface roughness Ra of 0.5 μm. .. Then, a refractory multilayer sheet was produced in the same manner as in Example 1 except that the obtained first base material was used.
The blast treatment in the examples was carried out by projecting alumina particles having a particle diameter of 80 to 200 μm onto a base material.
＜実施例３＞
第１の基材を、サンドブラスト処理を施したポリブチレンテレフタレートフィルム（厚さ０．１ｍｍ、Ｒａ：０．５μｍ）とした以外は実施例２と同様にして耐火多層シートを作製した。
<Example 3>
A refractory multilayer sheet was produced in the same manner as in Example 2 except that the first base material was a polybutylene terephthalate film (thickness 0.1 mm, Ra: 0.5 μm) that had been sandblasted.
＜実施例４＞
実施例１の第１の基材におけるＰＥＴフィルムを、ポリエチレンフィルムとした以外は実施例１と同様にして耐火多層シートを作製した。
<Example 4>
A refractory multilayer sheet was produced in the same manner as in Example 1 except that the PET film in the first base material of Example 1 was a polyethylene film.
＜実施例５＞
第２の基材の非積層面を細かめにサンドブラスト処理した白色ＰＥＴ（Ｒａ：０．４μｍ）とした以外は実施例２と同様にして耐火多層シートを作製した。
<Example 5>
A refractory multilayer sheet was produced in the same manner as in Example 2 except that the non-laminated surface of the second base material was finely sandblasted into white PET (Ra: 0.4 μm).
＜実施例６＞
第２の基材の非積層面を粗めにサンドブラスト処理した白色ＰＥＴ（Ｒａ：１μｍ）とした以外は実施例２と同様にして耐火多層シートを作製した。
<Example 6>
A refractory multilayer sheet was produced in the same manner as in Example 2 except that the non-laminated surface of the second base material was roughly sandblasted into white PET (Ra: 1 μm).
＜実施例７＞
熱膨張性樹脂組成物について、下記原料を用い押出成型により成型した以外は実施例２と同様にして耐火多層シートを作製した。なお基材を積層した後の厚みは２．２ｍｍであった。
<Example 7>
A refractory multilayer sheet was produced in the same manner as in Example 2 except that the heat-expandable resin composition was molded by extrusion molding using the following raw materials. The thickness after laminating the base materials was 2.2 mm.
（熱膨張性樹脂組成物）
クロロプレンゴム：ＭＴ−１０（デンカ社製） ８０質量部
熱膨張性黒鉛：ＣＡ６０Ｎ（エアウォーター社製）１００質量部
ポリリン酸アンモニウム：ＡＰ４２２（クラリアントケミカルズ社製）５０質量部
炭酸カルシウム：ＢＦ３００（白石カルシウム社製）３０質量部
(Thermal expandable resin composition)
Chloroprene rubber: MT-10 (manufactured by Denka) 80 parts by mass Thermally expandable graphite: CA60N (manufactured by Airwater) 100 parts by mass Ammonium polyphosphate: AP422 (manufactured by Clarianto Chemicals) 50 parts by mass Calcium carbonate: BF300 (Shiraishi calcium) 30 parts by mass
＜実施例８＞
熱膨張性樹脂組成物について、下記原料を用い押出成型により成型した以外は実施例２と同様にして耐火多層シートを作製した。なお基材を積層した後の厚みは０．８ｍｍであった。
<Example 8>
A refractory multilayer sheet was produced in the same manner as in Example 2 except that the heat-expandable resin composition was molded by extrusion molding using the following raw materials. The thickness after laminating the base materials was 0.8 mm.
（熱膨張性樹脂組成物）
エチレンビニルアセテート樹脂：ＥＶ４６０（三井ダウケミカル社製） ８０質量部
熱膨張性黒鉛：ＣＡ６０Ｎ（エアウォーター社製）１００質量部
ポリリン酸アンモニウム：ＡＰ４２２（クラリアントケミカルズ社製）５０質量部
炭酸カルシウム：ＢＦ３００（白石カルシウム社製）３０質量部
(Thermal expandable resin composition)
Ethylene vinyl acetate resin: EV460 (manufactured by Mitsui Dow Chemical Co., Ltd.) 80 parts by mass Thermally expandable graphite: CA60N (manufactured by Airwater) 100 parts by mass Ammonium polyphosphate: AP422 (manufactured by Clarianto Chemicals) 50 parts by mass Calcium carbonate: BF300 ( Shiraishi Calcium) 30 parts by mass
＜比較例１＞
ＰＥＴフィルム（市販品、厚さ：１００μｍ）を用い、これを第１の基材とした以外は実施例１と同様にして耐火多層シートを作製した。なお、このときの第１の基材の表面粗さは０．０５μｍであった。
<Comparative example 1>
A refractory multilayer sheet was produced in the same manner as in Example 1 except that a PET film (commercially available product, thickness: 100 μm) was used and this was used as the first base material. The surface roughness of the first base material at this time was 0.05 μm.
＜比較例２＞
ＰＥＴフィルム（市販品、厚さ：１００μｍ）を用い、熱膨張樹脂層が設けられない側の面の表面粗さを１００μｍとしてこれを第１の基材とした以外は実施例１と同様にして耐火多層シートを作製した。
<Comparative example 2>
The same as in Example 1 except that a PET film (commercially available product, thickness: 100 μm) was used and the surface roughness of the surface on the side where the thermal expansion resin layer was not provided was set to 100 μm and this was used as the first base material. A fireproof multilayer sheet was prepared.
＜搬送性の評価＞
図３に示すように、ゴム製のベルトを有するベルトコンベヤー３０上に耐火多層シート（２０ｃｍ×２０ｃｍ）１０を、第１の基材１２の熱膨張樹脂層が設けられてない側の面１２Ａが下面となるように置いた。耐火多層シートの第２の基材１６上に２０ｋｇの重り３２を載せて、耐火多層シート１０にフォースゲージ３４を取り付けて、これを真横（矢印方向）に引っ張り、重り３２が動き始めるときにゲージにかかる力を摩擦力（Ｎ）として観測した。結果を下記表１に示す。
なお、摩擦力は５〜２０Ｎであれば合格であり、８〜１５Ｎであると好ましい。
<Evaluation of transportability>
As shown in FIG. 3, a refractory multilayer sheet (20 cm × 20 cm) 10 is placed on a belt conveyor 30 having a rubber belt, and a surface 12A on the side of the first base material 12 on which the thermal expansion resin layer is not provided is provided. It was placed so that it was on the bottom surface. A 20 kg weight 32 is placed on the second base material 16 of the refractory multilayer sheet, a force gauge 34 is attached to the refractory multilayer sheet 10, and the force gauge 34 is pulled right beside (in the direction of the arrow), and the gauge is when the weight 32 starts to move. The force applied to the force was observed as the frictional force (N). The results are shown in Table 1 below.
If the frictional force is 5 to 20 N, it is acceptable, and preferably 8 to 15 N.
＜膨張倍率＞
試験片（長さ１００ｍｍ、幅１００ｍｍ）を実施例及び比較例で作製した耐火多層シートから切り出して電気炉に供給し、５００℃で３０分間加熱した。その後、試験片の厚さを測定し、（加熱後の試験片の厚さ／加熱前の試験片の厚さ）を計算し、その値が１３０％以上の場合を「Ａ」、１００％以上１３０％未満を「Ｂ」、７０％以上１００％未満を「Ｃ」と評価した。なお、熱膨張材の膨張倍率が７０％以上の耐火多層シートは建材として使用可能なものである。
<Expansion magnification>
The test piece (length 100 mm, width 100 mm) was cut out from the refractory multilayer sheet prepared in Examples and Comparative Examples, supplied to an electric furnace, and heated at 500 ° C. for 30 minutes. After that, the thickness of the test piece is measured, (thickness of the test piece after heating / thickness of the test piece before heating) is calculated, and when the value is 130% or more, "A", 100% or more. Less than 130% was evaluated as "B", and 70% or more and less than 100% was evaluated as "C". A refractory multilayer sheet having an expansion coefficient of 70% or more of the thermal expansion material can be used as a building material.
＜残渣硬さ＞
膨張倍率を測定した加熱後の試験片を圧縮試験機（カトーテック社製フィンガーフィリングテスター）に供給し、０．２５ｃｍ２の圧子で０．１ｃｍ／秒の速度で圧縮し、破断点応力を測定した。破断点応力が０．２ｋｇｆ／ｃｍ２以上である場合を「Ａ」、０．１５ｋｇｆ／ｃｍ２以上０．２ｋｇｆ／ｃｍ２未満である場合を「Ｂ」、０．１０以上０．１５未満である場合を「Ｃ」と評価した。なお、熱膨張材の残渣硬さが０．１０以上の耐火多層シートは建材として使用可能なものである。
<Residual hardness>
The heated test piece whose expansion ratio was measured was supplied to a compression tester (finger filling tester manufactured by Kato Tech), compressed with an indenter of 0.25 cm 2 at a speed of 0.1 cm / sec, and the breaking point stress was measured. did. Where stress at break is 0.2 kgf / cm 2 or more "A", the case is less than 0.15kgf / cm 2 or more 0.2 kgf / cm 2 "B", is less than 0.10 or more 0.15 One case was evaluated as "C". A refractory multilayer sheet having a residual hardness of 0.10 or more of the thermal expansion material can be used as a building material.
実施例１〜８はすべて摩擦力が合格であり、ゴム製のコンベアベルトに対し良好な搬送性を発揮し得ることがわかった。なお、実施例４は軟化点が他の実施例よりも低く、粉体塗装後の焼き付け温度については考慮する必要がある。また、実施例６は、第２の基材の表面粗さが大きいため、粉体塗装後の仕上がりで美観の面で多少劣る可能性がある。 It was found that all of Examples 1 to 8 passed the frictional force and could exhibit good transportability with respect to the rubber conveyor belt. The softening point of Example 4 is lower than that of other Examples, and it is necessary to consider the baking temperature after powder coating. Further, in Example 6, since the surface roughness of the second base material is large, the finish after powder coating may be slightly inferior in terms of aesthetics.
１０ 耐火多層シート
１２ 第１の基材
１２Ａ 熱膨張樹脂層１４が設けられていない側の面
１４ 熱膨張樹脂層
１６ 第２の基材
10 Fireproof multilayer sheet 12 First base material 12A Side surface on which the heat expansion resin layer 14 is not provided 14 Heat expansion resin layer 16 Second base material
Claims (6)
前記熱膨張樹脂層が樹脂及び熱膨張性黒鉛を含み、
第１の基材における前記熱膨張樹脂層が設けられていない側の面の表面粗さＲａが、０．２μｍ〜５０μｍである耐火多層シート。 A refractory multilayer sheet comprising a first base material, a heat-expandable resin layer, and a second base material in this order.
The heat-expandable resin layer contains resin and heat-expandable graphite, and contains
A refractory multilayer sheet having a surface roughness Ra of 0.2 μm to 50 μm on the side surface of the first base material on which the thermal expansion resin layer is not provided.
The fireproof multilayer sheet according to any one of claims 1 to 5, wherein the surface roughness Ra of the surface of the second base material on the side where the thermal expansion resin layer is not provided is 0.5 μm or less.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04142931A (en) * | 1990-10-03 | 1992-05-15 | Hayashi Telempu Co Ltd | Interior finishing material |
| JPH04312848A (en) * | 1991-04-11 | 1992-11-04 | Mitsui Toatsu Chem Inc | Manufacture of laminated sheet and its device |
| JPH11270019A (en) * | 1998-03-23 | 1999-10-05 | Sekisui Chem Co Ltd | Covering sheet for fire resistance |
| WO2017033461A1 (en) * | 2015-08-24 | 2017-03-02 | 日本ゼオン株式会社 | Thermally conductive sheet and production method therefor |
| JP2017202694A (en) * | 2016-01-21 | 2017-11-16 | 積水化学工業株式会社 | Fire-resisting multilayer sheet |
| JP2018020564A (en) * | 2016-07-25 | 2018-02-08 | 積水化学工業株式会社 | Refractory sheet |
-
2019
- 2019-05-20 JP JP2019094773A patent/JP7312016B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04142931A (en) * | 1990-10-03 | 1992-05-15 | Hayashi Telempu Co Ltd | Interior finishing material |
| JPH04312848A (en) * | 1991-04-11 | 1992-11-04 | Mitsui Toatsu Chem Inc | Manufacture of laminated sheet and its device |
| JPH11270019A (en) * | 1998-03-23 | 1999-10-05 | Sekisui Chem Co Ltd | Covering sheet for fire resistance |
| WO2017033461A1 (en) * | 2015-08-24 | 2017-03-02 | 日本ゼオン株式会社 | Thermally conductive sheet and production method therefor |
| JP2017202694A (en) * | 2016-01-21 | 2017-11-16 | 積水化学工業株式会社 | Fire-resisting multilayer sheet |
| JP2018020564A (en) * | 2016-07-25 | 2018-02-08 | 積水化学工業株式会社 | Refractory sheet |
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| JP7312016B2 (en) | 2023-07-20 |
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