JPS63168991A - Foamed polyester resin heating panel - Google Patents
Foamed polyester resin heating panelInfo
- Publication number
- JPS63168991A JPS63168991A JP31282686A JP31282686A JPS63168991A JP S63168991 A JPS63168991 A JP S63168991A JP 31282686 A JP31282686 A JP 31282686A JP 31282686 A JP31282686 A JP 31282686A JP S63168991 A JPS63168991 A JP S63168991A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- polyester resin
- conductive
- heating plate
- sheet
- 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
- 238000010438 heat treatment Methods 0.000 title claims description 52
- 229920001225 polyester resin Polymers 0.000 title claims description 15
- 239000004645 polyester resin Substances 0.000 title claims description 15
- 239000000835 fiber Substances 0.000 claims description 48
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 20
- 239000004917 carbon fiber Substances 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 17
- 210000004177 elastic tissue Anatomy 0.000 claims description 15
- 229920006305 unsaturated polyester Polymers 0.000 claims description 15
- 239000002657 fibrous material Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000005187 foaming Methods 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 5
- 150000001451 organic peroxides Chemical group 0.000 claims description 5
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical group CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 description 13
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 102100040428 Chitobiosyldiphosphodolichol beta-mannosyltransferase Human genes 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- -1 polybutylene ethylene terephthalate Polymers 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 101100491335 Caenorhabditis elegans mat-2 gene Proteins 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical class Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- AAOADXIHXYIOMT-UHFFFAOYSA-N 1,1'-biphenyl;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=CC=C1C1=CC=CC=C1 AAOADXIHXYIOMT-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- DYGOPFFOGFHOIB-UHFFFAOYSA-N methylperoxyethane Chemical compound CCOOC DYGOPFFOGFHOIB-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- QRKVRHZNLKTPGF-UHFFFAOYSA-N phosphorus pentabromide Chemical class BrP(Br)(Br)(Br)Br QRKVRHZNLKTPGF-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical class [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Landscapes
- Surface Heating Bodies (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、床、Ｒ暖房用、融雪用等の発熱板あるいは加
温用の容器資材等として好適に使用できる発泡ポリエス
テル樹脂発熱板に関するものである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a foamed polyester resin heating plate that can be suitably used as a heating plate for floors, R heating, snow melting, etc., or as a heating container material, etc. It is.
［従来技術］
従来、この種、床、Ｖ暖房用発熱板としては、上板と下
板の間に発熱体を組み込／’／、一体化したもの、前記
発熱体を電熱線とすると共に、これを下板に設置ｌた溝
内に収納配置し、更にこの電熱線」―にアルミ−ニウム
箔笠からなる金属箔均熱板を積層し、この−Ｆに−１−
板を積層−・体化したものが知らｈでいる。[Prior Art] Conventionally, this kind of heat generating plate for floor and V heating has a heating element built in between an upper plate and a lower plate, an integrated one, the heating element is a heating wire, and A metal foil heat equalizing plate made of an aluminum foil shade is laminated on this heating wire, and a heat equalizing plate made of aluminum foil is laminated on this
It is well known that the plates are laminated.
また、前記発熱体どして、基布に導電性塗ｆ１を塗布あ
るいは含浸したもの、繊維状導電体を基布に織り込んで
導電性をｆｔ ’７− したり、あるいは合成樹脂やゴ
ムに導電性材料を混入し、これを基布に塗布したものを
組み込んだものも知られている。The heating element may be made by coating or impregnating the base cloth with conductive coating f1, by weaving a fibrous conductor into the base cloth to make it conductive, or by making it conductive by synthetic resin or rubber. There are also known products that incorporate a synthetic material mixed in and coated on a base fabric.
［発明が解決しようとする問題点１
しかし、乍ら、これら従来の発熱板は、上板やＦ板が木
質材からなり、発熱体が１ζ板に設けた溝内に収納配置
され、下板によって積層されて組み付けられているため
生産性が極めて悪く、量産には適さずコスト高となり、
且つ定尺物の発熱パネルとしてしか製作できないもので
あった。また、上板、下板が木質材であるため床、壁暖
房用とじて長く使用した場合、収縮や変形する笠の寸法
安定性にも問題を有するものであった。[Problem to be solved by the invention 1 However, in these conventional heating plates, the upper plate and the F plate are made of wood, the heating element is housed in a groove provided in the 1ζ plate, and the lower plate is Because they are stacked and assembled, productivity is extremely low, making them unsuitable for mass production and resulting in high costs.
Moreover, it could only be manufactured as a fixed-sized heat generating panel. Furthermore, since the upper and lower plates are made of wood, there is also a problem with the dimensional stability of the shade, which shrinks and deforms when used for a long time for floor or wall heating.
本発明は、このような問題点に鑑みなされたもので、大
量生産可能で、月つ任意の長尺状の発熱板として製作が
容易であり、長期間に互って床、壁暖房あるいは融雪用
として使用しても収縮変形せず、電気絶縁性、耐蝕性、
耐水性にも優れた発泡ポリエステル樹脂発熱板を提供す
ることを目的とする。The present invention was developed in view of these problems, and can be mass-produced and can be easily manufactured as a long heat-generating plate in any desired length. It does not shrink or deform even when used for purposes, has electrical insulation, corrosion resistance,
The purpose of the present invention is to provide a foamed polyester resin heating plate that also has excellent water resistance.
［問題点を解決するための手段」
上記目的を達成するための本発明の構成は高弾性繊維マ
ットに導電性炭素繊維ステーブルと非導電性繊維状物を
バインダーの存在下でシート体とし、これに一対の電極
を設けた発熱シートと、非導電性繊維シートを重ね、こ
の積層物に不飽和ポリエステルに発泡剤と硬化剤及び硬
化促進剤を加えた混合液状物を均一に含まぜ、加熱して
発泡と共に硬化してなることをその要旨とするものであ
る。[Means for Solving the Problems] To achieve the above object, the present invention has a structure in which a highly elastic fiber mat, conductive carbon fiber stable and non-conductive fibrous material are formed into a sheet body in the presence of a binder, A heat generating sheet with a pair of electrodes and a non-conductive fiber sheet are layered on top of this, a liquid mixture of unsaturated polyester, a foaming agent, a curing agent and a curing accelerator is uniformly contained in this laminate, and heated. The gist is that it is formed by foaming and curing.
本発明に使用する高弾性繊維マットは非導電性−３〜
の繊維で例えば、合成繊維、天然繊維、ガラス繊維等で
織った繊布あるいは不織布のマット状のもので高度の回
復弾力性を有するものである。The high-elasticity fiber mat used in the present invention is a non-conductive fiber with a grade of -3 or higher, such as a woven or non-woven mat made of synthetic fibers, natural fibers, glass fibers, etc., and has a high degree of recovery elasticity. It is.
本発明では好ましくはポリエステル繊維、ポリオレフィ
ン繊維、ポリアミド繊維、アクリル繊維、レーヨン等が
挙げられるが、特にポリエステル繊維が優れた回復弾力
性を有するのでよく、その中でも潜在巻縮性を存するポ
リエステル複合繊維マットが性能が優れている。In the present invention, polyester fibers, polyolefin fibers, polyamide fibers, acrylic fibers, rayon, etc. are preferably used, but polyester fibers are particularly suitable because they have excellent recovery elasticity, and among them, polyester composite fiber mats with latent crimpability are used. has excellent performance.
このポリエステル複合繊維マットは、例えば５−スルホ
イソフタル酸共重合ポリエステルとポリブチレンチレフ
タレ−トを２成分とし、２成分の複合比が７０／３０〜
３０／７０．融点差が２０−４０℃である偏芯鞘型複合
繊維からなるウェッブの絡合点が低融合重合体で点結合
され”Ｃなるものであって、例えば、
（１）複合繊維の太さが１０〜２００ノｚ、好ましくは
２０〜５０μ、巻縮数が２５〜５０％、巻縮ピッチが１
０〜５０ケ／インチ、
（２）低融点重合体の融点が複合繊維の低融点−４＝
成分より４０〜９０゛Ｃ低く、マット重量に対する含有
量が３−３０重量％、
（３）マットの素性が１０〜４０（１１１３７ｇ、回復
弾性力が１０〜５０ｇ、
の特性を有するものが好ましく使用できる。This polyester composite fiber mat has two components, for example, 5-sulfoisophthalic acid copolymerized polyester and polybutylene ethylene terephthalate, and the composite ratio of the two components is 70/30 to 70/30.
30/70. The entanglement points of a web made of eccentric-sheath composite fibers with a melting point difference of 20-40°C are point-bonded with a low-fusion polymer to form "C", for example, (1) the thickness of the composite fibers is 10-200 noz, preferably 20-50μ, number of crimp 25-50%, crimp pitch 1
0 to 50 pieces/inch, (2) The melting point of the low melting point polymer is 40 to 90°C lower than the low melting point of the composite fiber - 4 = component, and the content is 3 to 30% by weight based on the weight of the mat, (3) Mat It is preferable to use a material having properties of 10 to 40 (11137 g, recovery elastic force of 10 to 50 g).
本発明では、この高弾性繊維マットに多数の繊維からな
る補強層を設けてもよい、例えばガラス、炭素、セラミ
ックス等の無機質及びポリエステル、ポリオレフィン、
ポリアミド、アクリル等の有機質繊維、これらの不織布
、織布等が用いられる。また、これら材質を組み合わせ
て使用することもでき、補強繊維におけるこの配列、層
数による構成は任意に選択してよい。In the present invention, this high elastic fiber mat may be provided with a reinforcing layer made of a large number of fibers, for example, inorganic materials such as glass, carbon, ceramics, polyester, polyolefin, etc.
Organic fibers such as polyamide and acrylic, nonwoven fabrics and woven fabrics thereof, and the like are used. Further, these materials can be used in combination, and the arrangement and number of layers of the reinforcing fibers may be arbitrarily selected.
本発明では、この補強層にはガラス繊維マットが好まし
く、優れた機械的強度、剛性の発熱板となすことができ
るのでよい。In the present invention, a glass fiber mat is preferable for this reinforcing layer because it can provide a heat generating plate with excellent mechanical strength and rigidity.
高弾性繊維マツ１〜にこの補強層を設ける手段は、予め
接着剤等で貼着する方法で設けることができるが、成形
時に高弾性繊維マットに補強層を重ね合わせる方法で設
けてもよい。第１図は、その補強層を、ｆＱけた高弾性
繊維マツ１〜の外観分解斜視図を示し、１は高弾性１ａ
維マツト、２は補強層である。The reinforcing layer can be provided on the high elastic fiber pine 1 by adhering it in advance with an adhesive or the like, but it may also be provided by superimposing the reinforcing layer on the high elastic fiber mat during molding. FIG. 1 shows an exploded perspective view of the appearance of high elastic fiber pine 1 to 1 whose reinforcing layer is of the order of fQ, 1 is a high elastic fiber 1a
The fiber mat 2 is a reinforcing layer.
次に、本発明に使用する発熱シートについて説明する。Next, the heat generating sheet used in the present invention will be explained.
第２図は、本発明に使用する発熱シートの部分拡大図で
あり、この発熱シート３は導電性炭素繊維ステーブル４
と非導電性繊維状物らがバインダー６の存在下でシート
体に形成され、これに第３図に示すように、一対の電［
ｉ７，７が設けられている。FIG. 2 is a partially enlarged view of the heat generating sheet used in the present invention, and this heat generating sheet 3 is connected to a conductive carbon fiber stable 4.
and a non-conductive fibrous material are formed into a sheet body in the presence of a binder 6, and a pair of electrically conductive [
i7,7 are provided.
導電性炭素繊維ステーブル４としては、現在製造されて
いるポリアクリロニトリル系、あるいはピッチ系等のも
のを用いることができ、その繊維長は通常ではｌＯ〜２
０ｍ輸である。また、炭素繊維ステーブル２の繊維径は
、５〜１０μのものが通常用いられる。As the conductive carbon fiber stable 4, currently manufactured polyacrylonitrile or pitch type materials can be used, and the fiber length is usually 1O~2.
The transport is 0m. Further, the fiber diameter of the carbon fiber stable 2 is usually 5 to 10 μm.
非導電性繊維状物らとしては、非導電性で繊維状であれ
ば如何なる種類でも用いることができ、例えばパルプ繊
維、木綿等の天然繊維、ナイロン、ポリエステル等の合
成繊維、ガラス繊維、石綿繊維等の無ｌＩ！１ｉｌａ維
、炭化珪素、金属酸化物等のウィスカー笠を挙げること
ができ、好ましくはガラスｍ維、パルプ繊維が用いられ
る。これら非導電性ｍ維状物５は、その種類によって異
なるが、例えばガラス繊維であれば繊維長５〜２ｆｌ＋
ｎ＋ａ 、繊維径５１ｆｌμ、パルプ繊維であれば繊維
長５〜２０＋ｕ＋、繊維径５・−］０７１のものが用い
られる。As the non-conductive fibrous material, any type of non-conductive fibrous material can be used, such as pulp fiber, natural fiber such as cotton, synthetic fiber such as nylon and polyester, glass fiber, and asbestos fiber. No such thing! Whisker caps such as 1ila fiber, silicon carbide, and metal oxide can be mentioned, and glass m fiber and pulp fiber are preferably used. These non-conductive m-fibrous materials 5 vary depending on their type, but for example, in the case of glass fibers, the fiber length is 5 to 2 fl+
n+a, fiber diameter 51flμ, fiber length 5 to 20+u+, fiber diameter 5·-]071 if it is pulp fiber.
非導電性繊維状物５と導電性炭素繊維ステーブル４との
混合量は、導電性炭素繊維ステーブル４が有する固有の
電気抵抗値にもとづき、本発明により得られる発熱板に
如何なる電気抵抗値を付与するかにより任意に決定する
ことができる。The amount of the non-conductive fibrous material 5 and the conductive carbon fiber stable 4 to be mixed is determined based on the inherent electric resistance value of the conductive carbon fiber stable 4, and the amount of electric resistance to be determined by the heating plate obtained by the present invention. It can be arbitrarily determined depending on whether the
炭素繊維ステーブルが同一比抵抗の時は、混合量が小さ
い程、発熱温度が低下する。通常では炭素繊維ステーブ
ルの混合量は、炭素繊維ステーブル士非導電性繊維状物
の１０〜６０重景％であり、好ましくは２０〜３０重量
％である。When carbon fiber stables have the same specific resistance, the smaller the mixing amount, the lower the heat generation temperature. Usually, the amount of carbon fiber stabilizer mixed is 10 to 60% by weight, preferably 20 to 30% by weight of the carbon fiber stabilizer and non-conductive fibrous material.
炭素繊維ステーブルの混合量が１０重ｆ％に満たないと
通常の発熱板を得るには導電性炭素繊維の−７＝
比固有抵抗は退任とならざるを得す、炭素繊維偏在によ
る熱過高の危険を招来することになり、また、６０重量
％を越えると、炭素繊維の混入量過多となって好ましい
発泡した発熱板が得られないので好ましくない。If the mixed amount of carbon fiber stable is less than 10% by weight, the specific resistivity of the conductive carbon fiber must be reduced to -7 to obtain a normal heat generating plate. Moreover, if it exceeds 60% by weight, the amount of carbon fiber mixed in will be too large, making it impossible to obtain a foamed heating plate, which is not preferable.
バインダー６は、炭素繊維ステーブル４と非導電性繊維
状物５を相互に固着せし、ぬる機能を有しており、具体
的には、カゼイン、ポリビニルアルコール系糊、ポリア
クリル系、ポリアミド系、または、ポリエチレンオキシ
ド系の糊、カルテツク、変性澱粉等を挙げることができ
、好ましくはカゼイン、ポリビニルアルコール系糊であ
る。また、バ、インダー６の使用量は、炭素繊維ステー
ブルと非導電性繊維の合計重量の５〜１０重量％である
。バインダー６の使用１が５重量％に満たないと、接着
強皮剥となり、１０重足％を越えると好ましい発泡した
発熱板が得られないので好ましくないかかるバインダー
６は、例えば導電性炭素繊維ステーフルと非導電性繊維
状物が抄紙されるときに添加され、これらの交絡部を接
着、固定する。The binder 6 has a function of fixing and wetting the carbon fiber stable 4 and the non-conductive fibrous material 5 to each other, and specifically binds casein, polyvinyl alcohol glue, polyacrylic glue, polyamide glue, etc. Alternatively, examples thereof include polyethylene oxide-based glue, Caltech, modified starch, etc., and casein and polyvinyl alcohol-based glue are preferred. Further, the amount of the inder 6 used is 5 to 10% by weight of the total weight of the carbon fiber stable and the non-conductive fiber. If the amount of the binder 6 used is less than 5% by weight, the adhesive will peel off, and if it exceeds 10% by weight, a preferable foamed heat generating plate cannot be obtained, which is undesirable. Non-conductive fibrous materials are added during paper making to bond and fix these intertwined portions.
。このように得られたシート体には難燃剤を添加するこ
とちり能である、この難燃剤には、脂肪族、芳香族化合
物の臭素化物、臭化第２リン、臭素酸ソーダ、臭化亜鉛
、臭化アンモニウム等の臭素系難燃剤、ポリリン酸アン
モニウム、リン酸ビフェニル、 ＰＯＣｌ３． ＰＣＩ
ｒ、Ｈ３１’０２ 、 ＰＯＢｒ３笠のリン系難燃剤、
Ｃ，Ｈ，Ｃ）ＩｃＩ２、ＮＨ，ＣＩ等の塩素系難燃剤、
ＩＩ ３ＢＯ３，１１２０３等のホウ素系、グアニジン
、ジフェニルアミン、硫安等のアミン系、シアヌル酸メ
ラミン等が用いられる。. A flame retardant can be added to the sheet body thus obtained.This flame retardant includes brominated aliphatic and aromatic compounds, phosphoric bromide, sodium bromate, and zinc bromide. , brominated flame retardants such as ammonium bromide, ammonium polyphosphate, biphenyl phosphate, POCl3. PCI
r, H31'02, POBr3kasa phosphorus flame retardant,
C, H, C) Chlorine flame retardants such as IcI2, NH, CI,
Boron-based materials such as II 3BO3, 11203, amine-based materials such as guanidine, diphenylamine, and ammonium sulfate, and melamine cyanurate are used.
このような難燃剤は、バインダーと共に抄紙時に添加、
混合されても良いし、抄紙した後に吹き付けたり、ある
いは抄紙した後に難燃剤含有液中に浸積して難燃剤処理
される。Such flame retardants are added together with binders during paper making.
They may be mixed, or they may be treated with a flame retardant by being sprayed after paper making, or by being immersed in a flame retardant-containing liquid after paper making.
電極７．７としては、銀塗料等の導電性塗料、または炭
素繊維フィラメントと導電性塗料の組み合わせが用いら
れ、あるいは銅線、銅箔、その他の導電性金属線、金属
箔を用いることができる。As the electrode 7.7, a conductive paint such as silver paint or a combination of carbon fiber filament and conductive paint is used, or a copper wire, copper foil, other conductive metal wire, or metal foil can be used. .
このようにして得られた本発明で使用できる発熱シート
３の性状を次に例示する。The properties of the heat generating sheet 3 that can be used in the present invention thus obtained are illustrated below.
発熱シートの厚さ・・・０．２〜０．３１１１１ノｌ
単位重量・・・３０〜５０ｇ／励２不燃性炭素含有量
・・・１５〜３０ｇ／ｍ２空 間 率
・・・０．１へ０．２ワット密度 ・・
・０．０５〜０．１５Ω／Ｃ１２縦方向 ・・・１１
〜１２
抵抗の方向性
横方向 ・・弓、０
面抵抗偏差率 ・・・１０％以下以上述べたよう
に本発明に使用する発熱シート３は炭素繊維ステーブル
と非導電性繊維状物で抄紙されているので、炭素繊維の
種類およびその使用量を適宜選定することにより発熱シ
ート３の電気抵抗値を目的に応じて自由に変化させるこ
とができる。Thickness of heat generating sheet...0.2 to 0.31111 nol
Unit weight: 30-50g/excitation 2 non-flammable carbon content
...15-30g/m2 space ratio
...0.1 to 0.2 watt density...
・0.05~0.15Ω/C12 Vertical direction...11
〜12 Resistance direction: Lateral direction: Bow, 0 Sheet resistance deviation rate: 10% or more As mentioned above, the heat generating sheet 3 used in the present invention is made of carbon fiber stable and non-conductive fibrous material. Therefore, by appropriately selecting the type of carbon fiber and the amount used, the electrical resistance value of the heat generating sheet 3 can be freely changed depending on the purpose.
次に、この発熱シート３に重ねる一Ｊｔ＋導電性繊維マ
ット３０は非導電性の繊維からなる例えば、ガラス繊維
、合成樹脂繊維の織布あるいは不織布のマット状のもの
で、本発明では好ましくはガラス繊維マットが使用でき
る。このマットは単数枚を使用してもよいが複数枚を重
ね使用することも可能である。Next, the conductive fiber mat 30 overlaid on the heat generating sheet 3 is made of non-conductive fibers, such as a mat of glass fiber, synthetic resin fiber woven fabric or non-woven fabric. Fiber mats can be used. A single mat may be used, but it is also possible to use a plurality of mats stacked together.
本発明の発泡ポリエステル樹脂発熱板は、上記高弾性繊
維マット１に発熱シート３と非導電性繊維マット３０を
重ねた積層物を使用して製造される第４図は、その本発
明の発熱板を製造する製造装置の一実施例を示す図であ
る。The foamed polyester resin heat generating plate of the present invention is manufactured using a laminate in which the above-mentioned high elastic fiber mat 1 is laminated with a heat generating sheet 3 and a non-conductive fiber mat 30. FIG. 4 shows the heat generating plate of the present invention. 1 is a diagram showing an example of a manufacturing apparatus for manufacturing.
図において、Ｆは高弾性繊維マット１と発熱シート３及
び非導電性繊維３０を連続的に繰り出す繰出し装置であ
る。In the figure, F is a feeding device that continuously feeds out the high elastic fiber mat 1, heat generating sheet 3, and non-conductive fibers 30.
含浸装置りは不飽和ポリエステルに発泡剤と硬化促進剤
、要すれば整泡剤、分解促進剤等を加えた液タンク８と
硬化剤として有機パーオキサイドと無水の有機酸の液タ
ンク９が設けられている。The impregnation device is equipped with a liquid tank 8 containing unsaturated polyester with a foaming agent, a curing accelerator, and if necessary a foam stabilizer, a decomposition accelerator, etc., and a liquid tank 9 containing organic peroxide and anhydrous organic acid as curing agents. It is being
この液タンク８．９のそれぞれの液は定量ポンプ１０．
１１によって所定量が混合器１２に送られ混合される。Each liquid in this liquid tank 8.9 is supplied to a metering pump 10.
11, a predetermined amount is sent to mixer 12 and mixed.
混合された水工存在の混合液状物１３は散布器１４によ
って常温下で均一に積層物に含浸さぜる得られた液状物
含浸繊維体】５は成形用加熱トンネル金型Ｈに導かれる
。The mixed liquid material 13 of the waterworks is uniformly impregnated into the laminate at room temperature by a sprayer 14.The obtained liquid material-impregnated fiber body 5 is led to a heating tunnel mold H for forming.
成形用加熱トンネル金型Ｈは、入口に水で冷却する冷却
部１６を設け、金型１（の加熱部は複数区画されそれぞ
れ独立して温度調節が可能な加熱器１７が設けられた内
面がクロムメッキされたトンネル状のものである。The heating tunnel mold H for molding has a cooling part 16 that is cooled with water at the entrance, and the heating part of the mold 1 has a plurality of sections, each of which has an inner surface equipped with a heater 17 that can independently adjust the temperature. It is a chrome plated tunnel shaped thing.
液状物含浸繊維体］５は入口で常温程度に冷却し、加熱
部に入って加熱器１７によって加熱され、ポリエステル
が発泡し、最後の加熱器１７に至って硬化が完了する。The liquid material-impregnated fiber] 5 is cooled to about room temperature at the entrance, enters the heating section, is heated by the heater 17, the polyester foams, and reaches the last heater 17 to complete curing.
得られた発熱板１８は引き抜き装置Ｋによって引き抜か
れる。The obtained heat generating plate 18 is pulled out by a pulling device K.
引き抜き装置には、表面が粗となった例えば、ゴム製の
エンドレスベルト１９ａ、 １９ｂからなり、発熱板１
８を上下から挟んで連続的に引き抜かれる。The pulling device consists of endless belts 19a and 19b made of rubber, for example, with a rough surface, and a heat generating plate 1.
8 is continuously pulled out from above and below.
この引き抜き速度は液状物含浸繊維体１５が最後の加熱
器１７で丁度硬化が完了するよう調節されている。引き
抜かれた発熱板１８は所望の寸法の長さにカッター２０
によって切断される。This drawing speed is adjusted so that the liquid-impregnated fiber body 15 is just completely cured in the final heater 17. The pulled out heating plate 18 is cut into a desired length using a cutter 20.
disconnected by.
成形用加熱トンネル金型Ｈには発熱板１８が金型Ｉ］内
面に付着しないよう、且つ光沢ある表面の発熱板を得る
ため発熱板１８の上下面と金型内面の間に例えば、ポリ
エステル製のエンドレスベルト２１ａ、２１１）を設け
ることができる。The heating tunnel mold H for molding is equipped with a heating plate 18 made of polyester, for example, between the upper and lower surfaces of the heating plate 18 and the inner surface of the mold in order to prevent the heating plate 18 from adhering to the inner surface of the mold I and to obtain a heating plate with a glossy surface. endless belts 21a, 211) can be provided.
このように得られた発泡ポリエステル樹脂発熱板】８の
電極７．７の末端に保護端子を固定し、これにリード線
が連結される。これはそのままの状態で床、壁暖房用と
して、また融雪用として使用できる。A protective terminal was fixed to the end of the electrode 7.7 of the foamed polyester resin heating plate 8 thus obtained, and a lead wire was connected to this. This can be used as is for floor and wall heating, and for snow melting.
ここで本発明に使用する不飽和ポリエステルとは、マレ
イン酸またはフマル酸のような不飽和酸とグリコ ル類
とを反応させると、いわゆるポリエステルを生ずるが、
このポリエステルはスチレンのようなｌｉ体に溶解する
。この溶液は、これに適当な硬化剤及び硬化促進剤を加
えると、ポリエステルと＃を量体との間で付加重合反応
を起こし、熱硬化性の樹脂を成長する。これが、こわゆ
る不飽和ポリエステルといわれる樹脂である。Here, the unsaturated polyester used in the present invention is a so-called polyester that is produced when an unsaturated acid such as maleic acid or fumaric acid is reacted with a glycol.
This polyester is soluble in li forms such as styrene. When a suitable curing agent and curing accelerator are added to this solution, an addition polymerization reaction occurs between the polyester and the #mer, and a thermosetting resin is grown. This resin is called a stiff unsaturated polyester.
不飽和ポリエステルにあっては、−上記の溶液から樹脂
への変化が極めて短い時間に行なわれる。In the case of unsaturated polyesters, the above-mentioned transformation from solution to resin takes place in a very short time.
この特性を利用して、不飽和ポリエステル樹脂発泡体を
作ろうとする試みがなされてきた。しかし、不飽和ポリ
エステルは硬化挙動が他の樹脂に比べ非常に異なり、そ
れ故発泡させることは困難であった。即ち、不飽和ポリ
エステルは液状で流動性のものであるが、重合反応の進
行に伴ない、その粘度が短時間に急激に増大してゲル化
するので、発泡に適した粘度を有する時間が極めて短か
く、発泡剤を使用しても発泡剤の分解をこの時間に対応
することが極めて困難なためである。Attempts have been made to utilize this property to produce unsaturated polyester resin foams. However, unsaturated polyesters have very different curing behavior than other resins and are therefore difficult to foam. In other words, unsaturated polyester is liquid and fluid, but as the polymerization reaction progresses, its viscosity rapidly increases and gels. This is because even if a blowing agent is used, it is extremely difficult to decompose the blowing agent within this period of time.
本発明者は、かかる問題を解決するため鋭意研究の結果
、不飽和ポリエステルを発泡する際、発泡剤に炭酸水素
アンモニウム粉末を使用し、硬化剤に有機パーオキサイ
ドと硬化促進剤及び無水の有機酸を混合した水手存在の
混合液状物を含ませ加熱して発泡と共に硬化する方法を
発明し、先に本出願人において特願昭６１−０５０００
１号（昭和６１年３月７日出願）、特願昭６１−０８６
２５６号（昭和６１年４月１４日出願）、特願昭６＋−
１９３０３６号（昭１ａ６１年８月１９日出願）に出願
している。As a result of intensive research to solve this problem, the inventor of the present invention has found that when foaming unsaturated polyester, ammonium hydrogen carbonate powder is used as a blowing agent, organic peroxide is used as a curing agent, a curing accelerator, and an anhydrous organic acid. The applicant invented a method of foaming and curing the mixture by heating it and foaming it with a liquid mixture of water.
No. 1 (filed on March 7, 1986), patent application 1986-086
No. 256 (filed on April 14, 1986), patent application 1986+-
No. 193036 (filed on August 19, 1988).
本発明に使用する発泡剤は好ましくは炭酸水素アンモニ
ウム粉末がよく、これは微粉化された粒径が３０μ以下
のものがよい。゛この炭酸水素アンモニウム粉末の使用
量は、所望する発熱板の発泡倍率によって任意に選択で
きるが、不飽和ポリエステル１００重量部に対し、０．
１〜２０重量部、好ましくは０２〜１０重量部が使用さ
れる。The blowing agent used in the present invention is preferably ammonium hydrogen carbonate powder, which has a finely divided particle size of 30 μm or less.゛The amount of ammonium bicarbonate powder to be used can be arbitrarily selected depending on the desired expansion ratio of the heating plate, but it is 0.00 parts by weight per 100 parts by weight of unsaturated polyester.
1 to 20 parts by weight are used, preferably 02 to 10 parts by weight.
不飽和ポリエステルの重縮合反応による硬化に使用され
る硬化剤は、有機パーオキサイドが使用される。これに
はケトンパーオキサイド系（例えば、メチルエチルケト
ンパーオキサイド）０．ハイドロパーオキサイド系（例
えば、クメンハイドロパーオキサイド）、ジアシルパー
オキサイド系（例えば、ベンゾイル、パーオキサイド〉
、パーオキシジカーボネート系（例〕ば、ジイソプロピ
ルパーオキサイド）、パーオキシエステル系（例えば、
ｔ−ブヂルバーオキンアセテート）等の有機過酸化物を
挙げることができ、これらの２種以上を組み合わせて使
用することもできる。The curing agent used for curing the unsaturated polyester by polycondensation reaction is an organic peroxide. This includes ketone peroxide systems (eg methyl ethyl ketone peroxide) 0. Hydroperoxide type (e.g. cumene hydroperoxide), diacyl peroxide type (e.g. benzoyl, peroxide)
, peroxydicarbonate type (e.g. diisopropyl peroxide), peroxyester type (e.g.
For example, organic peroxides such as t-butilveroxene acetate) can be used, and two or more of these can also be used in combination.
この硬化剤に併用する硬化促進剤は、例えばナフテン酸
コバルト、オクトエ酸コバルト、ナフテン酸マンガン、
ナフテン酸銅、ナフテン酸亜鉛、ラウリルメルカプタン
、ジメチルアニリン、トリエタノールアミン、ジエチレ
ン１−リアミン、ピリジン、ピペリジン等を挙げること
ができ、これらの２種以上を組み合わせて使用してもよ
い。Curing accelerators used in combination with this curing agent include, for example, cobalt naphthenate, cobalt octoate, manganese naphthenate,
Copper naphthenate, zinc naphthenate, lauryl mercaptan, dimethylaniline, triethanolamine, diethylene 1-lyamine, pyridine, piperidine, etc. can be mentioned, and two or more of these may be used in combination.
この好適な混合量の条件は、不飽和ポリエステル１００
重量部に対し、前記硬化剤は０８５〜２．０重量部、前
記硬化促進剤は０．０１〜０．５重量部が使用される。The conditions for this suitable mixing amount are as follows: 100% unsaturated polyester
The curing agent is used in an amount of 085 to 2.0 parts by weight, and the curing accelerator is used in an amount of 0.01 to 0.5 parts by weight.
本発明では好ましくは硬化剤とくでメチルエチルケトン
パーオキサイドが使用でき、これに併用する硬化促進剤
としてはナフテン酸コバルトが好適で炭酸水素アンモニ
ウムと組み合わせて使用した場合、発熱板の成形作業性
がよく、且つ均一微細な気泡の発泡が得られるのでよい
。In the present invention, methyl ethyl ketone peroxide can preferably be used as a curing agent, and cobalt naphthenate is suitable as a curing accelerator to be used in combination with this, and when used in combination with ammonium hydrogen carbonate, the molding workability of the heating plate is good. Moreover, it is good because uniform and fine foaming of cells can be obtained.
また、本発明では前記硬化剤及び硬化促進剤と共に無水
の有機酸も使用でき、例えば無水の酢酸またはアクリル
酸が使用できる。この混合量は不飽和ポリエステル１０
０重量部に対し、０．１〜３．０重量部が使用される。Further, in the present invention, an anhydrous organic acid can also be used together with the curing agent and curing accelerator, such as acetic anhydride or acrylic acid. This mixing amount is 10% of unsaturated polyester.
0.1 to 3.0 parts by weight are used relative to 0 parts by weight.
更に、要すれば整泡剤、離型剤、着色剤等を必要に応じ
使用することも可能である。Furthermore, it is also possible to use a foam stabilizer, a mold release agent, a coloring agent, etc., if necessary.
第５図は、かくして得られた発熱板１８の分解斜視図で
あり、発熱シート３の下部には高弾性繊維マット１の高
発泡樹脂の断熱層１ａが形成され、上部には非導電性繊
緋シート３０の低発泡樹脂の電気絶縁層３０ａが形成さ
れている。FIG. 5 is an exploded perspective view of the heat generating plate 18 obtained in this way, in which a heat insulating layer 1a of highly foamed resin of the highly elastic fiber mat 1 is formed at the bottom of the heat generating sheet 3, and a non-conductive fiber is formed at the top. An electrically insulating layer 30a of a low foam resin of a scarlet sheet 30 is formed.
［発明の作用コ
本発明の発泡ポリエステル樹脂発熱板は、高弾性繊維マ
ット１に非導電性炭素繊維ステーブル４と非導電性繊維
状物５をバインダー６の存在下でシー１一体としたもの
に、一対の電［１７，７を設けた発熱シート３と、非導
電性繊維シート３０を重ね、この積層物に飽和ポリエス
テルに発泡剤と硬化剤及び硬化促進剤を加えた混合液状
物１３を均一に合成ぜ、加熱し発泡と共に硬化して製造
したものなので、不飽和ポリエステルの混合液状物１３
が積層物に含浸し易く、且つ発泡の際、分解ガスが積層
物内に均一に分散されるので均一微細なポリウムのある
軽量な発熱板が得られる。そして積層物が補強材となり
機械的強度、剛性の優れた発熱板となすことができると
共に、発熱シート３の下部には高弾性繊維マット１の高
発泡樹脂の断熱層１ａが形成され、上部には非導電性繊
維シート３０の低発泡樹脂の電気絶縁層３０ａが形成さ
れているので低発泡樹脂の絶縁層３０ａから効率よく加
熱される、また、これが最初から一体的に製造され、切
断して任意の長尺寸法にできるので、大量生産に適し、
−々組み付ける作業も不要である。[Function of the Invention] The foamed polyester resin heating plate of the present invention has a highly elastic fiber mat 1, a non-conductive carbon fiber stable 4, and a non-conductive fibrous material 5 integrated into a sheet 1 in the presence of a binder 6. A heat generating sheet 3 provided with a pair of electric currents 17, 7 and a non-conductive fiber sheet 30 are stacked on top of each other, and a liquid mixture 13 of saturated polyester, a foaming agent, a curing agent and a curing accelerator is added to this laminate. It is manufactured by uniformly synthesizing, heating, foaming and curing, so it is a liquid mixture of unsaturated polyester 13.
It is easy to impregnate the laminate, and during foaming, the cracked gas is uniformly dispersed within the laminate, resulting in a lightweight heat-generating plate with uniformly fine polygon. The laminate serves as a reinforcing material and can be used as a heat generating plate with excellent mechanical strength and rigidity. At the bottom of the heat generating sheet 3, a heat insulating layer 1a of highly foamed resin of the highly elastic fiber mat 1 is formed, and on the top. Since the electrically insulating layer 30a of the non-conductive fiber sheet 30 is made of a low foam resin, it is efficiently heated from the insulating layer 30a of the low foam resin. Suitable for mass production as it can be made into any length dimension.
-No assembly work is required.
この発熱板１８の表面には更にプラスチックフィルムや
塗料を施し２電気絶縁性、装飾性を高めることも可能で
ある。It is also possible to further apply a plastic film or paint to the surface of the heating plate 18 to improve electrical insulation and decorative properties.
［発明の効果］
以上説明したように本発明の発熱板は、従来のように上
板と下板との間に発熱体を一々組み込んで一体化したも
のとは異なり、一体的に製造され、しかも任意の長尺寸
法のものが得られるので大量生産に適し安価に提供でき
る。そして木質材と異なり長期間使用しても収縮したり
変形することなく、一般の暖房用、保温用は勿論、畜産
用、園芸用等の従来のものとは側底使用不可能であった
新分野にまで広範囲に利用することができる。[Effects of the Invention] As explained above, the heat generating plate of the present invention is manufactured in one piece, unlike the conventional one in which the heat generating elements are integrated between the upper plate and the lower plate. Moreover, since it can be made in any length, it is suitable for mass production and can be provided at low cost. Unlike wood materials, it does not shrink or deform even after long-term use, and is a new material that cannot be used for general heating, heat retention, livestock farming, gardening, etc. It can be used in a wide range of fields.
［実施例］ 以下、本発明を実施例に基づいて更に詳細に説明する。[Example] Hereinafter, the present invention will be explained in more detail based on examples.
第４図に示す製造装置を使用し本発明の発熱板を製造し
た。繰り出し装置Ｆに、高弾性繊維マット１（帝人社製
、高弾性不織布、嵩性・・・２０ｃｓ３゜回復弾性力・
・・３０ｇ）の両面にガラス繊維マット２（旭ガラスフ
ァイバー社製、コンデニアスストランド）を設けたロー
ルと、炭素繊維ステープルとガラス繊維状物をバインダ
ーの存在下で抄紙したシート体に電極を設けた発熱シー
ト３（新富土製紙社製・・・面発熱紙、ワラ）・密度
０．１ Ｗ ／ ｃ ｍ ２）を設けたロール及びガラ
ス繊維マット３０（旭ガラスファイバー社製、コンテニ
アスストランド）を設けたロールを使用し、これから引
き出された積層物に、不飽和ポリエステル（日本ユビカ
社製、ユビカ７５９５） １００重量部に対し、粒径１
ｏμ以下の炭酸水素アンモニウム粉末３重量部と６％ナ
フテン酸コバルト０．２重り部及びシリコンオイル（ト
ーレシリコン社製、１・−レシリコン５Ｒ−１９０）
０５重量部、内部離型剤（デュポンファーイースト社製
、ゼレックＮＥ）０．５重量部、ステアリン酸１重量部
を加えた液タンク８とメチルエチルパーオキサイド（日
本樹脂社製、バーメックＮ）１重量部に無水酢酸２重量
部を加えた液タンク９から定量ポンプ１０１１によって
送られ、混合器１２によって混合された混合液状物１３
を散布器１４によって均一に含浸量が約６０％になるよ
うに含浸せしめた。この液状物含浸繊維体１５を引っ張
って成形用加熱トンネル金型Ｈ（全長１．１５０＋ｓｍ
Ｘ巾１５０ｍｍ ｘ高さ１２＋ｍ）に導いた。そして
、それぞれの加熱器１７（４，５に駿）の温度は７０〜
８０℃に調節し、加熱して、発泡させｆｉ後の加熱器１
７で硬化が完了する速度で引っ張り、得られた発熱板１
８は引抜き装置Ｋ（引抜き強さ１．２Ｔ）の引抜きベル
ト１９ａ、 １９ｂに挟み、最後の加熱器１７で硬化が
完了する速度で連続的に引き抜いた。そして１．８ｍの
長さにカッター２０で切断し、断面が１５０ｍｍ Ｘ
１２＋ａｍ、長さ１．８−の本発明の発泡ポリエステル
樹脂発熱板を得な。The heat generating plate of the present invention was manufactured using the manufacturing apparatus shown in FIG. High elastic fiber mat 1 (manufactured by Teijin, high elastic nonwoven fabric, bulk...20 cs 3° recovery elastic force...
Electrodes were provided on a roll with glass fiber mat 2 (manufactured by Asahi Glass Fiber Co., Ltd., Condensed Strand) on both sides of . Heat-generating sheet 3 (manufactured by Shintomi Paper Co., Ltd., surface heat-generating paper, straw), density
0.1 W/cm2) and a roll equipped with glass fiber mat 30 (manufactured by Asahi Glass Fiber Co., Ltd., Continuous Strand) were used, and the laminate drawn from this was coated with unsaturated polyester (Japanese). (Manufactured by Yubika, Yubika 7595) Particle size 1 per 100 parts by weight
3 parts by weight of ammonium hydrogen carbonate powder of 0 μ or less, 0.2 parts by weight of 6% cobalt naphthenate, and silicone oil (manufactured by Toray Silicon Co., Ltd., 1·-resilicon 5R-190)
0.5 parts by weight of internal mold release agent (DuPont Far East Co., Ltd., Zerec NE), a liquid tank 8 containing 1 part by weight of stearic acid, and methyl ethyl peroxide (Vermec N, manufactured by Nippon Jushi Co., Ltd.) 1 A liquid mixture 13 containing 2 parts by weight of acetic anhydride is sent from a liquid tank 9 by a metering pump 1011 and mixed by a mixer 12.
was uniformly impregnated with the sprayer 14 so that the amount of impregnation was approximately 60%. This liquid-impregnated fiber body 15 is pulled into a heating tunnel mold H for molding (total length 1.150+sm).
(width 150mm x height 12+m). The temperature of each heater 17 (4 and 5) is 70~
Heater 1 after adjusting to 80°C, heating and foaming
The heat generating plate 1 obtained by pulling at a speed at which curing is completed in step 7
8 was sandwiched between the drawing belts 19a and 19b of the drawing device K (pulling strength: 1.2T), and was continuously drawn out at a speed until curing was completed by the final heater 17. Then cut it to a length of 1.8m with a cutter 20, and the cross section is 150mm
Obtain a foamed polyester resin heating plate of the present invention having a length of 12+ am and a length of 1.8-.
この得られた発熱板の電極の末端に保護端子を固定し、
これにリード線を連結し通電したところ発熱板の表面温
度が約８０℃になり好ましく加温された。A protective terminal is fixed to the end of the electrode of this heating plate,
When a lead wire was connected to this and electricity was applied, the surface temperature of the heat generating plate reached about 80° C., indicating a favorable heating.
第１図は、本発明に使用する高弾性繊維マットの外観分
解斜視図、第２図は、発熱シートの部分拡大図、第３図
は、電極を設けた発熱シートの外観図である。第４図は
、本発明の発熱板を製造する製造装置の一実施例を示す
図である。第５図は、本発明で得られた発熱板の分解斜
視図である。
１・・・高弾性繊維マット２・・・補強層 ３・・・発
熱シート ３０・・非導電性繊維シート ４・・・導電
性炭素繊維ステーブル ５・・・非導電性繊維状物 ６
・・・バインダー ７・・・電［１８，９・・・液タン
ク １０］１・・・定量ポンプ １２・・混合器１３・
・・混合液状物 １４・・・散布器 】５・・・液状物
含浸繊維体 １７・・・加熱器 １８・・・発熱板 １
９ ａ、１９ｂ・・・エンドレスベルト ２０・・・カ
ッター １８・・・断熱層 ３０ａ ・電気絶縁層 Ｆ
・・・繰出し装置５Ｄ・・・含浸袋Ｗ Ｈ・・・金型
Ｋ・・・引抜き装置
特許出卯人 有限会社 野沢工務店
第５図
手続補正書（方式）
％式％
１、事件の表示
昭和６１年特許願第３１２８２６号
２、発明の名称
発泡ポリエステル樹脂発熱板
３、補正をする者
事件との関係 特許出願人
住所 富山県下新用郡入善町青木６０１〒９３９−０６
８０７６５−７４−０２８２別紙の通りFIG. 1 is an exploded perspective view of the appearance of a highly elastic fiber mat used in the present invention, FIG. 2 is a partially enlarged view of a heat-generating sheet, and FIG. 3 is an external view of a heat-generating sheet provided with electrodes. FIG. 4 is a diagram showing an embodiment of the manufacturing apparatus for manufacturing the heat generating plate of the present invention. FIG. 5 is an exploded perspective view of the heat generating plate obtained by the present invention. 1... High elastic fiber mat 2... Reinforcement layer 3... Heat generating sheet 30... Non-conductive fiber sheet 4... Conductive carbon fiber stable 5... Non-conductive fibrous material 6
... Binder 7... Electric [18,9... Liquid tank 10] 1... Metering pump 12... Mixer 13.
...Mixed liquid material 14...Scatterer]5...Liquid material impregnated fiber body 17...Heater 18...Heating plate 1
9 a, 19b... Endless belt 20... Cutter 18... Heat insulation layer 30a ・Electrical insulation layer F
...Feeding device 5D...Impregnated bag W H...Mold
K... Drawing device patent issuer Nozawa Construction Co., Ltd. Figure 5 Procedure amendment (method) % formula % 1. Indication of the case Patent application No. 312826 filed in 1985 2. Name of the invention Foamed polyester resin heating plate 3. Relationship with the person making the amendment Patent applicant address: 601 Aoki, Nyuzen-cho, Shimoshinyo-gun, Toyama Prefecture 939-06
80765-74-0282 As per attached sheet
Claims (1)
導電性繊維状物をバインダーの存在下でシート体とし、
これに一対の電極を設けた発熱シートと、非導電性繊維
シートを重ね、この積層物に不飽和ポリエステルに発泡
剤と硬化剤及び硬化促進剤を加えた混合液状物を均一に
含ませ、加熱して発泡と共に硬化してなることを特徴と
する発泡ポリエステル樹脂発熱板。 ２）非導電性繊維状物がガラス繊維又はパルプ繊維であ
る特許請求の範囲第１項記載の発泡ポリエステル樹脂発
熱板。 ３）発熱シートの消費電力が０．０５〜０．１５Ｗ／ｃ
ｍ＾２である特許請求の範囲第１項、第２項記載の発泡
ポリエステル樹脂発熱板。 ４）非導電性繊維シートがガラス繊維マットである特許
請求の範囲第１項ないし第３項記載の発泡ポリエステル
樹脂発熱板。 ５）発泡剤が炭酸水素アンモニウムである特許請求の範
囲第１項ないし第４項記載の発泡ポリエステル樹脂発熱
板。 ６）硬化剤が有機パーオキサイドである特許請求の範囲
第１項ないし第５項記載の発泡ポリエステル樹脂発熱板
。 ７）硬化促進剤がナフテン酸コバルトである特許請求の
範囲第１項ないし第６項記載の発泡ポリエステル樹脂発
熱板。[Claims] 1) A highly elastic fiber mat made of a conductive carbon fiber stable and a non-conductive fibrous material in the presence of a binder as a sheet body,
A heating sheet with a pair of electrodes and a non-conductive fiber sheet are layered on top of this, and this laminate is uniformly impregnated with a liquid mixture of unsaturated polyester, a foaming agent, a curing agent, and a curing accelerator, and then heated. A foamed polyester resin heating board characterized by being formed by foaming and curing. 2) The foamed polyester resin heating plate according to claim 1, wherein the non-conductive fibrous material is glass fiber or pulp fiber. 3) Power consumption of heat generating sheet is 0.05-0.15W/c
The foamed polyester resin heating plate according to claims 1 and 2, wherein the heating plate is m^2. 4) The foamed polyester resin heating plate according to any one of claims 1 to 3, wherein the non-conductive fiber sheet is a glass fiber mat. 5) The foamed polyester resin heating plate according to claims 1 to 4, wherein the foaming agent is ammonium hydrogen carbonate. 6) The foamed polyester resin heating plate according to any one of claims 1 to 5, wherein the curing agent is an organic peroxide. 7) The foamed polyester resin heating plate according to claims 1 to 6, wherein the curing accelerator is cobalt naphthenate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31282686A JPS63168991A (en) | 1986-12-27 | 1986-12-27 | Foamed polyester resin heating panel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31282686A JPS63168991A (en) | 1986-12-27 | 1986-12-27 | Foamed polyester resin heating panel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63168991A true JPS63168991A (en) | 1988-07-12 |
Family
ID=18033887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31282686A Pending JPS63168991A (en) | 1986-12-27 | 1986-12-27 | Foamed polyester resin heating panel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63168991A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4824916U (en) * | 1971-08-07 | 1973-03-24 | ||
| JPS55108195A (en) * | 1979-02-14 | 1980-08-19 | Sekisui Chemical Co Ltd | Method of manufacturing panel heating plate |
| JPS55166892A (en) * | 1979-05-28 | 1980-12-26 | Sekisui Chemical Co Ltd | Panel heater |
| JPS5792777A (en) * | 1980-11-29 | 1982-06-09 | Sekisui Chemical Co Ltd | Method of producing panel heater |
-
1986
- 1986-12-27 JP JP31282686A patent/JPS63168991A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4824916U (en) * | 1971-08-07 | 1973-03-24 | ||
| JPS55108195A (en) * | 1979-02-14 | 1980-08-19 | Sekisui Chemical Co Ltd | Method of manufacturing panel heating plate |
| JPS55166892A (en) * | 1979-05-28 | 1980-12-26 | Sekisui Chemical Co Ltd | Panel heater |
| JPS5792777A (en) * | 1980-11-29 | 1982-06-09 | Sekisui Chemical Co Ltd | Method of producing panel heater |
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