JP2000171148A - Cooling device - Google Patents
Cooling deviceInfo
- Publication number
- JP2000171148A JP2000171148A JP10348220A JP34822098A JP2000171148A JP 2000171148 A JP2000171148 A JP 2000171148A JP 10348220 A JP10348220 A JP 10348220A JP 34822098 A JP34822098 A JP 34822098A JP 2000171148 A JP2000171148 A JP 2000171148A
- Authority
- JP
- Japan
- Prior art keywords
- heat insulating
- box
- foam
- foaming agent
- rigid polyurethane
- 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
- 238000001816 cooling Methods 0.000 title claims abstract description 12
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000004088 foaming agent Substances 0.000 claims abstract description 63
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 58
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 58
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- UXPOJVLZTPGWFX-UHFFFAOYSA-N pentafluoroethyl iodide Chemical compound FC(F)(F)C(F)(F)I UXPOJVLZTPGWFX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000004888 barrier function Effects 0.000 claims abstract description 20
- 239000011810 insulating material Substances 0.000 claims abstract description 13
- 239000012792 core layer Substances 0.000 claims description 30
- 238000009413 insulation Methods 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 abstract description 31
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 abstract description 3
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006260 foam Substances 0.000 description 61
- 229920005862 polyol Polymers 0.000 description 55
- 150000003077 polyols Chemical class 0.000 description 55
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 38
- 239000000463 material Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 22
- -1 polyethylene terephthalate Polymers 0.000 description 22
- 239000012948 isocyanate Substances 0.000 description 17
- 150000002513 isocyanates Chemical class 0.000 description 17
- 238000005187 foaming Methods 0.000 description 15
- 239000007809 chemical reaction catalyst Substances 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000004721 Polyphenylene oxide Substances 0.000 description 11
- 229920000570 polyether Polymers 0.000 description 11
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 10
- 239000004745 nonwoven fabric Substances 0.000 description 10
- 238000005057 refrigeration Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 8
- VKABKQBHBBROCU-UHFFFAOYSA-N 2-(2,2,3-trimethylpiperazin-1-yl)ethanamine Chemical compound CC1NCCN(CCN)C1(C)C VKABKQBHBBROCU-UHFFFAOYSA-N 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000011800 void material Substances 0.000 description 6
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- 229940029284 trichlorofluoromethane Drugs 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 3
- XTGYEAXBNRVNQU-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-iodopropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)I XTGYEAXBNRVNQU-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- HOVAGTYPODGVJG-UVSYOFPXSA-N (3s,5r)-2-(hydroxymethyl)-6-methoxyoxane-3,4,5-triol Chemical compound COC1OC(CO)[C@@H](O)C(O)[C@H]1O HOVAGTYPODGVJG-UVSYOFPXSA-N 0.000 description 1
- RKOUFQLNMRAACI-UHFFFAOYSA-N 1,1,1-trifluoro-2-iodoethane Chemical compound FC(F)(F)CI RKOUFQLNMRAACI-UHFFFAOYSA-N 0.000 description 1
- QATBCALBGXOFPI-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoro-1-iodopropane Chemical compound FC(F)C(F)(F)C(F)(F)I QATBCALBGXOFPI-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- AXNUJYHFQHQZBE-UHFFFAOYSA-N 3-methylbenzene-1,2-diamine Chemical compound CC1=CC=CC(N)=C1N AXNUJYHFQHQZBE-UHFFFAOYSA-N 0.000 description 1
- DGRGLKZMKWPMOH-UHFFFAOYSA-N 4-methylbenzene-1,2-diamine Chemical compound CC1=CC=C(N)C(N)=C1 DGRGLKZMKWPMOH-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241001147388 Uncia Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
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- 230000006837 decompression Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000004619 high density foam Substances 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
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- PDJAZCSYYQODQF-UHFFFAOYSA-N iodine monofluoride Chemical compound IF PDJAZCSYYQODQF-UHFFFAOYSA-N 0.000 description 1
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- 239000005001 laminate film Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 1
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- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- OURNLUUIQWKTRH-UHFFFAOYSA-N oxirane;phenol Chemical compound C1CO1.OC1=CC=CC=C1.OC1=CC=CC=C1 OURNLUUIQWKTRH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Refrigerator Housings (AREA)
- Laminated Bodies (AREA)
Abstract
(57)【要約】
【課題】発泡剤としてクロロフルオロカーボンやハイド
ロクロロフルオロカーボンを全く使用せず、その代替と
してペンタフルオロヨウドエタン発泡剤およびシクロペ
ンタン発泡剤を用いて、地球環境に優しい、省エネ,省
資源の保冷装置の提供にある。
【解決手段】保冷装置の断熱箱体１の外箱２と内箱３と
の間の断熱壁を構成する断熱材が、ぺンタフルオロヨウ
ドエタンと水の混合発泡剤を用いた独立構造の気泡を有
する硬質ポリウレタンフォームと、ガスバリア性の密閉
封着型断熱パネル４と、シクロペンタンと水の混合発泡
剤で発泡された硬質ポリウレタンフォーム６により構成
されていることを特徴とする保冷装置。
(57) [Summary] [PROBLEMS] To use no chlorofluorocarbon or hydrochlorofluorocarbon as a blowing agent at all, and to use a pentafluoroiodoethane blowing agent and a cyclopentane blowing agent as a substitute for the blowing agent. The purpose of the present invention is to provide a resource cooling device. A heat insulating material constituting a heat insulating wall between an outer box (2) and an inner box (3) of a heat insulating box (1) of a cold storage device is an air bubble of an independent structure using a mixed foaming agent of pentafluoroiodoethane and water. , A rigid polyurethane foam having a gas barrier property, a hermetically sealed heat insulating panel 4, and a rigid polyurethane foam 6 foamed with a mixed foaming agent of cyclopentane and water.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、冷凍冷蔵庫、冷凍
庫、ショーケース、冷凍室などに用いる硬質ポリウレタ
ンフォームの断熱箱体で構成した保冷装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cooling device comprising a rigid polyurethane foam heat insulating box used for a refrigerator, a freezer, a showcase, a freezer, and the like.
【０００２】[0002]
【従来の技術】従来、冷凍冷蔵庫、冷凍庫、ショーケー
ス、冷凍室などの保冷装置に使用している断熱部材は、
外箱と内箱の空間に硬質ポリウレタンフォームを充填す
るだけで、容易に形成できる安価な断熱材を用いてき
た。こうした保冷装置として、家庭用冷凍冷蔵庫を例に
説明をする。2. Description of the Related Art Insulation members conventionally used in refrigerators such as refrigerators, freezers, showcases, and freezers are:
Inexpensive heat insulators that can be easily formed simply by filling the space between the outer box and the inner box with a rigid polyurethane foam have been used. A home refrigerator-freezer will be described as an example of such a refrigerator.
【０００３】硬質ポリウレタンフォームは、ポリオール
成分とイソシアネート成分を発泡剤、触媒、整泡剤など
の存在下で反応させることにより得られる。これまでの
発泡剤としては、ガス熱伝導率の低く、難分解性のクロ
ロフルオロカーボン（ＣＦＣ）の一種であるトリクロロ
モノフルオロメタン（特開昭５９−８４９１３号公報）
を発泡材に用いた断熱部材に使用されてきた。しかし、
上記ＣＦＣが大気中に放出されると成層園のオゾン層破
壊、並びに、その温室効果による地表の温度上昇の要因
となることが分かり、近年、これらの代替品の選択，研
究が進められている。A rigid polyurethane foam is obtained by reacting a polyol component with an isocyanate component in the presence of a foaming agent, a catalyst, a foam stabilizer and the like. As a conventional foaming agent, trichloromonofluoromethane, which is a kind of chlorofluorocarbon (CFC) having low gas thermal conductivity and difficult to decompose (Japanese Patent Application Laid-Open No. 59-84913).
Has been used for a heat insulating member using a foam material. But,
It has been found that the release of CFCs into the atmosphere causes destruction of the ozone layer in the stratosphere and increases the surface temperature due to its greenhouse effect. In recent years, selection and research on these alternatives have been advanced. .
【０００４】上記代替発泡剤として、現在、ハイドロク
ロロフルオロカーボン（ＨＣＦＣ）の１種である１,１
−ジクロロ−１−モノフルオロエタン（特開平３−２５
８８２３号公報）が、冷凍冷蔵庫の断熱部材用発泡剤に
用いられてきたが、オゾン層破壊係数がゼロでないため
規制の対象となり、２００３年には全廃の予定になって
いる。As an alternative foaming agent, 1,1 which is a kind of hydrochlorofluorocarbon (HCFC) is presently used.
-Dichloro-1-monofluoroethane (JP-A-3-25
No. 8823) has been used as a foaming agent for heat insulating members of refrigerators and refrigerators. However, since the ozone depletion potential is not zero, it is subject to regulation and is scheduled to be completely abolished in 2003.
【０００５】一方、オゾン層破壊係数がゼロのノンフロ
ン系発泡剤は、欧州を中心に炭化水素系化合物（特開平
３−１５２１６０号公報）への代替が活発となり、それ
に伴い日本でもシクロペンタン発泡剤が冷凍冷蔵庫等の
断熱材に使用され始めた。On the other hand, non-fluorocarbon blowing agents having an ozone layer depletion potential of zero have been actively replaced by hydrocarbon compounds (JP-A-3-152160) mainly in Europe. Began to be used for insulation materials such as refrigerators and refrigerators.
【０００６】しかし、シクロペンタンはこれまでの発泡
剤に比べ、ガスの熱伝導率が高く断熱性能が大きく劣る
と云う問題がある。However, cyclopentane has a problem that the thermal conductivity of the gas is high and the heat insulation performance is significantly inferior to the conventional foaming agents.
【０００７】近年では、熱伝導率の低い代替発泡剤とし
てヨウ素を有するフルオロヨウドカーボンを用い紫外線
不透過処理を施した樹脂製の発泡体（特開平８−１１０
１５３号公報）、フッ素化ヨウ化炭化水素、パーフルオ
ロアルケンや水素含有フッ化モルフォリン誘導体を発泡
体として用いたもの（特開平８−１６９９７６号公
報）、真空断熱パネル（特開平７−１１００９７号公
報）等の断熱材が提案されている。[0007] In recent years, resin foams which have been subjected to ultraviolet opacity treatment using fluoroiodocarbon containing iodine as an alternative foaming agent having a low thermal conductivity (Japanese Patent Laid-Open No. 8-110)
No. 153), those using a fluorinated iodinated hydrocarbon, a perfluoroalkene or a hydrogen-containing morpholine derivative as a foam (Japanese Patent Application Laid-Open No. 8-169996), and a vacuum insulation panel (Japanese Patent Application Laid-Open No. 7-110097). Publication) has been proposed.
【０００８】[0008]
【発明が解決しようとする課題】しかし、前記ヨウ素を
有するフルオロヨウドカーボン発泡剤であるトリフルオ
ロヨウドメタン、トリフルオロヨウドエタン、テトラフ
ルオロヨウドエタン、ヘプタフルオロヨウドプロパン、
ヘキサフルオロヨウドプロパンなどを用いた硬質ポリウ
レタンフォームには、既に、規制されて全廃となってい
るトリクロロフルオロメタン（ＣＦＣ−１１）のよう
に、その熱伝導率が１３.５ｍＷ／ｍＫ以下の特性が得
られないと云う問題がある。However, the iodine-containing fluoroiodocarbon blowing agents trifluoroiodomethane, trifluoroiodoethane, tetrafluoroiodoethane, heptafluoroiodopropane,
Rigid polyurethane foam using hexafluoroiodopropane or the like has a property of having a thermal conductivity of 13.5 mW / mK or less, like trichlorofluoromethane (CFC-11), which has already been regulated and completely abolished. There is a problem that it cannot be obtained.
【０００９】また、フルオロヨウドカーボンは、ヨウ素
の光分解が起こり易く、空気中の水分や酸素の影響によ
り熱伝導率の経時劣化が大きくなること、内箱材料に安
価な汎用ＡＢＳ樹脂（アクリロニトリル、ブタジェンゴ
ム、スチレン共重合体）を用いると、ケミカルアタック
により低温歪が発生すること、分子量の大きいヨウ素を
含むため発泡効率が劣り、従来発泡剤に比べて２倍以上
の発泡剤量が必要であるなどの問題がある。In addition, fluoroiodocarbon is liable to undergo photodecomposition of iodine, greatly deteriorates the thermal conductivity with time due to the influence of moisture and oxygen in the air, and is inexpensive general-purpose ABS resin (acrylonitrile, When butadiene rubber and styrene copolymer are used, low-temperature distortion is caused by chemical attack, and the foaming efficiency is inferior because of containing iodine having a high molecular weight, and the amount of the foaming agent is required to be twice or more as compared with the conventional foaming agent. There is such a problem.
【００１０】更にまた、フルオロヨウドカーボンは、合
成原料であるヨウ素が地球上に少ないため、冷凍冷蔵庫
の断熱部材全部に用いる発泡剤量の確保が困難なこと、
シクロペンタン発泡剤に比べて約１０倍以上とコスト高
であるなどの問題もある。[0010] Furthermore, fluoroiodocarbon has a low amount of iodine as a synthetic raw material on the earth, so that it is difficult to secure a sufficient amount of a foaming agent to be used for all heat insulating members of a refrigerator-freezer.
There is also a problem that the cost is about 10 times or more higher than the cyclopentane blowing agent.
【００１１】こうしたことから、フルオロヨウドカーボ
ンを冷凍冷蔵庫の発泡剤に適用するには、断熱パネルの
回収やリサイクルなどが可能な技術開発が望まれてい
る。[0011] In view of the above, in order to apply fluoroiodocarbon to a foaming agent for refrigerators and refrigerators, it is desired to develop a technology capable of collecting and recycling an insulating panel.
【００１２】一方、熱伝導率が１３.５ｍＷ／ｍＫ以下
と優れた公知の断熱パネルには、気泡が連続構造を有す
る真空断熱パネルがある。On the other hand, a known heat insulating panel having a thermal conductivity as low as 13.5 mW / mK or less is a vacuum heat insulating panel having a continuous structure of air bubbles.
【００１３】しかし、真空断熱パネルは発泡ポリウレタ
ンのコア材が、減圧時に発生する水分やガス成分を吸収
して減圧真空度の劣化を防止するゲッタ剤の挿入や、優
れた断熱性能を得るため０.０１〜０.００１ｍｍＨｇと
云う高真空度の排気が必要である。真空断熱パネルは、
内部圧力が連続構造の気泡を通して均一に所定圧力まで
減圧する必要があり、高減圧化による長時間排気が不可
欠となり、生産効率の低下や高コスト化の問題がある。
さらには、真空断熱パネルには高真空度を保持するため
にラミネートフィルムが必要で、該ラミネートフィルム
は使用中に僅かなピンホールが発生しても熱伝導率が急
激に上昇し、冷凍冷蔵庫などの断熱効果が失われ、欠陥
製品となる恐れがある。However, in the vacuum insulation panel, since the core material of the foamed polyurethane absorbs moisture and gas components generated at the time of decompression and inserts a getter agent to prevent the deterioration of the degree of vacuum under reduced pressure, and obtains excellent heat insulation performance, Evacuation at a high vacuum of 0.01 to 0.001 mmHg is required. Vacuum insulation panels
It is necessary that the internal pressure be uniformly reduced to a predetermined pressure through bubbles having a continuous structure, and long-term evacuation by increasing the pressure is indispensable, resulting in a problem of lowering production efficiency and increasing costs.
Furthermore, a vacuum insulation panel requires a laminated film to maintain a high degree of vacuum. Even if a slight pinhole is generated during use, the thermal conductivity of the laminated film rapidly increases, and a refrigerator or the like is used. May lose the heat insulating effect, resulting in defective products.
【００１４】また、密閉封着パネル間の断熱，接着に用
いるシクロペンタン発泡剤を用いた硬質ポリウレタンフ
ォームでは、密閉封着型断熱パネルを外箱と内箱との壁
内空間に挿入して使用されるため、冷凍冷蔵庫の壁内空
間の狭隙間化に伴ない、ウレタンフォーム形成時に流動
しにくいために均一フォームが形成されにくく、冷凍冷
蔵庫の天井部、底部、背面部、ハンドル部、ヒンジ部の
全体密度や、コア層密度が大きく異なり、また、最終充
填部近傍の樹脂化やボイド発生などにより、歩留りが低
下すると云う問題がある。In the case of a rigid polyurethane foam using a cyclopentane foaming agent used for heat insulation and adhesion between the hermetically sealed panels, the hermetically sealed type heat insulating panel is used by being inserted into the space in the wall between the outer box and the inner box. As a result, as the space in the wall of the refrigerator becomes narrower, it is difficult to flow when urethane foam is formed, so that it is difficult to form a uniform foam, and the ceiling, bottom, back, handle, hinges of the refrigerator are formed. In addition, there is a problem that the overall density and the core layer density are greatly different from each other, and the yield decreases due to resinification and void generation near the final filling portion.
【００１５】上記の点から、シクロペンタン発泡剤を用
いた硬質ポリウレタンフォームには、低密度で高流動性
の材料が必要となっている。In view of the above, a rigid polyurethane foam using a cyclopentane blowing agent requires a material having a low density and a high fluidity.
【００１６】本発明者らは、トリクロロフルオロメタン
（ＣＦＣ−１１）のように平均温度０℃で、熱伝導率が
１３.５ｍＷ／ｍＫ以下の断熱材を、代替発泡剤のフル
オロヨウドカーボンで達成させること、さらに、フルオ
ロヨウドカーボンの問題である熱伝導率の経時劣化、発
泡剤の使用量低減、安価な汎用ＡＢＳ樹脂の使用、発泡
剤の回収・再利用などについて鋭意検討を進めた。The present inventors have achieved a heat insulating material such as trichlorofluoromethane (CFC-11) having an average temperature of 0 ° C. and a thermal conductivity of 13.5 mW / mK or less by using fluoroiodocarbon as an alternative foaming agent. In addition, intensive studies were conducted on the problems of fluoroiodocarbon, such as deterioration of thermal conductivity with time, reduction in the amount of foaming agent used, use of inexpensive general-purpose ABS resin, and recovery and reuse of the foaming agent.
【００１７】まず、内箱と外箱の壁内空間にフルオロヨ
ウドカーボン発泡剤を直接箱体に発泡充填することやフ
ルオロヨウドカーボンとシクロペンタンなどの混合系発
泡剤の使用では、課題を両立して解決することが難しい
ことが分かってきた。このことから、本発明のフルオロ
ヨウドカーボン発泡剤を用いた断熱パネルは、独立構造
の気泡を有する密閉封着型断熱パネルとすることにより
熱伝導率の経時劣化、発泡剤の使用量低減、安価な汎用
ＡＢＳ樹脂の使用、単品発泡剤による回収・再利用の課
題が解決可能なことが分かった。[0018] First, foaming and filling of a box with a fluoroiodocarbon foaming agent directly into the inner space of the wall of the inner box and the outer box, and the use of a mixed foaming agent such as fluoroiodocarbon and cyclopentane have both problems. Has proven difficult to solve. From this, the thermal insulation panel using the fluoroiodocarbon foaming agent of the present invention is a sealed thermal insulation panel having cells of independent structure, whereby the thermal conductivity deteriorates with time, the amount of the foaming agent used is reduced, and the cost is reduced. It has been found that the problem of using a general-purpose ABS resin and recovering and reusing with a single-piece foaming agent can be solved.
【００１８】さらには、真空断熱パネルの高減圧化のた
めの長時間排気の問題や、ラミネートフィルムのピンホ
ール化による異常な熱伝導率上昇についての問題も一挙
に解決するため、フルオロヨウドカーボン発泡剤を用い
た断熱パネルの熱伝導率を種々検討した結果、トリクロ
ロフルオロメタンのように１３.５ｍＷ／ｍＫ以下の優
れた熱伝導率を示す特性は、どうしても得られないこと
が分かってきた。Further, in order to solve the problem of long-term exhaustion for increasing the pressure of the vacuum insulation panel and the problem of an abnormal increase in thermal conductivity due to the formation of pinholes in the laminate film, fluoroiodide carbon foam is used. As a result of various studies on the thermal conductivity of the heat insulating panel using the agent, it has been found that a characteristic exhibiting an excellent thermal conductivity of 13.5 mW / mK or less, such as trichlorofluoromethane, cannot be obtained.
【００１９】本発明の目的は、上記の課題を解決し、熱
伝導率が１３.５ｍＷ／ｍＫ以下の密閉封着型断熱パネ
ルとシクロペンタン発泡剤を用いた低密度・高流動性の
硬質ポリウレタンフォームを組合わせた、地球環境に優
しい、低コスト化高歩留まりを図った断熱箱体で構成さ
れた保冷装置を提供することにある。An object of the present invention is to solve the above-mentioned problems, and to provide a low-density and high-flow hard polyurethane using a hermetically sealed heat insulating panel having a thermal conductivity of 13.5 mW / mK or less and a cyclopentane blowing agent. An object of the present invention is to provide a cold storage device composed of a heat-insulating box which is combined with a foam, is environmentally friendly, is low in cost, and has a high yield.
【００２０】[0020]
【課題を解決するための手段】本発明者らは、種々のフ
ルオロヨウドカーボン化合物を合成すると共に、密閉封
着型断熱パネルを作製し熱伝導率を評価した結果、例え
ばトリフルオロヨウドメタンは沸点が−２２℃と低過ぎ
てフォーム充填が困難なこと、ヘプタフルオロヨウドプ
ロパンは沸点が４０℃と高く発泡効率が劣ること、熱伝
導率が１３.５ｍＷ／ｍＫ以下のフルオロヨウドカーボ
ン化合物がほとんど見当らない状況の中で、発泡剤に使
用できる化合物としてペンタフルオロヨウドエタンを見
出すことができた。Means for Solving the Problems The inventors of the present invention synthesized various fluoroiodocarbon compounds, produced a hermetically sealed heat insulating panel, and evaluated the thermal conductivity. As a result, for example, trifluoroiodomethane had a boiling point of trifluoroiodomethane. Is too low as −22 ° C., making foam filling difficult, heptafluoroiodopropane has a boiling point as high as 40 ° C., resulting in inferior foaming efficiency, and almost all fluoroiodocarbon compounds having a thermal conductivity of 13.5 mW / mK or less are found. Under no circumstances, pentafluoroiodoethane could be found as a compound that can be used as a blowing agent.
【００２１】即ち、ペンタフルオロヨウドエタン発泡剤
は１３℃の低沸点を示し、発泡効率や熱伝導率特性もト
リクロロフルオロメタン（ＣＦＣ−１１：沸点２０℃以
上）のように優れた特性を有することから、ペンタフル
オロヨウドエタンの発泡剤を用いた独立構造の気泡を有
する硬質ポリウレタンフォームと、密閉封着型断熱パネ
ルと、地球環境に優しいシクロペンタン発泡剤の硬質ポ
リウレタンフォームを組合わせた断熱材とすることで、
本発明を完成するに至った。本発明の要旨は次のとおり
である。That is, the pentafluoroiodoethane foaming agent has a low boiling point of 13 ° C., and has excellent foaming efficiency and thermal conductivity characteristics such as trichlorofluoromethane (CFC-11: boiling point of 20 ° C. or more). From, a rigid polyurethane foam having cells of independent structure using a pentafluoroiodoethane foaming agent, a hermetically sealed insulation panel, and a heat insulating material combining a hard polyurethane foam of a cyclopentane foaming agent that is environmentally friendly by doing,
The present invention has been completed. The gist of the present invention is as follows.
【００２２】〔１〕 保冷装置の断熱箱体の外箱と内箱
との間の断熱壁を構成する断熱材が、ぺンタフルオロヨ
ウドエタンと水の混合発泡剤を用いた独立構造の気泡を
有する硬質ポリウレタンフォームと、ガスバリア性の密
閉封着型断熱パネルと、シクロペンタンと水の混合発泡
剤で発泡された硬質ポリウレタンフォームにより構成さ
れていることを特徴とする保冷装置。[1] The heat insulating material constituting the heat insulating wall between the outer box and the inner box of the heat insulating box body of the cooling device is made of an air bubble having an independent structure using a mixed foaming agent of pentafluoroiodoethane and water. A cold insulation device comprising: a rigid polyurethane foam having a gas barrier, a hermetically sealed heat insulating panel having gas barrier properties, and a rigid polyurethane foam foamed with a mixed foaming agent of cyclopentane and water.
【００２３】〔２〕 前記断熱箱体の断熱壁を構成する
断熱材が、外箱鉄板内面側にガスバリア性の密閉封着型
断熱パネルで遮蔽され、シクロペンタンおよび水の混合
発泡剤で発泡された硬質ポリウレタンフォームが充填さ
れている前記の保冷装置。[2] A heat insulating material constituting the heat insulating wall of the heat insulating box is shielded on the inner surface side of the outer case iron plate by a gas barrier airtight sealing type heat insulating panel, and foamed with a mixed foaming agent of cyclopentane and water. The cooling device as described above, which is filled with a rigid polyurethane foam.
【００２４】〔３〕 前記密閉封着型断熱パネルが、ガ
スバリア性の袋中にゲッタ剤および／またはアルカリ金
属の水酸化物を一緒に挿入した断熱パネルである前記の
保冷装置。[3] The cooling device as described above, wherein the hermetically sealed heat insulating panel is a heat insulating panel in which a getter agent and / or an alkali metal hydroxide are inserted into a gas barrier bag.
【００２５】〔４〕 前記シクロペンタンと水の混合発
泡剤で発泡された硬質ポリウレタンフォームが、コア層
密度３１〜３４ｋｇ／ｍ3である前記の保冷装置。[4] The cooling device as described above, wherein the rigid polyurethane foam foamed with the mixed blowing agent of cyclopentane and water has a core layer density of 31 to 34 kg / m 3 .
【００２６】〔５〕 前記断熱箱体の内箱が、アクリロ
ニトリル，ブタジエンゴム，スチレン共重合体からなる
汎用ＡＢＳ樹脂で構成されている前記の保冷装置。[5] The above-described cooling device, wherein the inner box of the heat-insulating box is made of a general-purpose ABS resin made of acrylonitrile, butadiene rubber, and styrene copolymer.
【００２７】[0027]
【発明の実施の形態】本発明において、密閉封着した独
立気泡を有するペンタフルオロヨウドエタン発泡剤の断
熱パネルは、ガスバリア性の袋中にポリオール成分を基
本原料とし、ペンタフルオロヨウドエタンと水、整泡
剤、反応触媒の存在下でイソシアネートとの反応によ
り、硬質ポリウレタンフォームの発泡充填を行い、熱融
着して密閉封着したものである。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an insulating panel of a pentafluoroiodoethane foaming agent having closed cells which are hermetically sealed is provided by using a polyol component as a basic raw material in a gas barrier bag, pentafluoroiodoethane and water, The rigid polyurethane foam is subjected to foam filling by reaction with an isocyanate in the presence of a foam stabilizer and a reaction catalyst, and is heat-sealed and hermetically sealed.
【００２８】ガスバリア性袋としてのフィルムは、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
などの芳香族ポリエステル、ポリエチレン、ポリプロピ
レンなどのポリオレフィン、ポリアクリロニトリル、ポ
リアミド、ポリビニルアルコール、ポリメチルメタクリ
レート、アクリロニトリル−ブタジエン−スチレン共重
合体、および／または、フィルム上にアルミニウム箔や
セラミック箔を設けた包装材などを使用した。The film as the gas barrier bag is made of an aromatic polyester such as polyethylene terephthalate or polybutylene terephthalate, a polyolefin such as polyethylene or polypropylene, polyacrylonitrile, polyamide, polyvinyl alcohol, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer. And / or a packaging material provided with an aluminum foil or a ceramic foil on a film was used.
【００２９】また、ペンタフルオロヨウドエタン発泡剤
の断熱パネルは、ガスバリア性の包装材よりなる袋中に
封入可能な形状であれば特に限定はなく、パネル寸法の
一例として縦および横が約５００ｍｍ、厚さが約２０ｍ
ｍのものを挙げることができる。しかしながら、縦およ
び横の長さは用途により例えば２００ｍｍ〜８００ｍｍ
の広範囲において適宜変更されるが、厚さは通常１０〜
３０ｍｍの範囲である。There is no particular limitation on the insulating panel made of a pentafluoroiodoethane foaming agent as long as it can be sealed in a bag made of a gas barrier packaging material. About 20m thick
m. However, the vertical and horizontal lengths are, for example, 200 mm to 800 mm depending on the application.
The thickness is usually changed from 10 to 10
The range is 30 mm.
【００３０】さらには、ガスバリア性の袋中に発泡充填
した断熱パネルを、ゲッタ剤やアルカリ金属などと密封
すると、熱伝導率の低減をさらに図ることができる。こ
れはウレタンフォームの気泡中に存在する熱伝導率の高
い炭酸ガスを吸着する効果と考えられる。その際、ガス
を吸着，除去するゲッタ剤としては、モレキュラーシー
ブ、シリカゲル、酸化カルシウム、ゼオライト、活性炭
などがあり、特に、炭酸ガスを吸着，除去するアルカリ
金属としては水酸化カリウム、水酸化ナトリウム、水酸
化リチウムなど、あるいは、これらをポリオレフィン樹
脂などでカプセル化したものを用いることもできる。Further, when the heat insulating panel foamed and filled in the gas barrier bag is sealed with a getter agent or an alkali metal, the thermal conductivity can be further reduced. This is considered to be an effect of adsorbing carbon dioxide gas having a high thermal conductivity existing in bubbles of urethane foam. At that time, getter agents for adsorbing and removing gas include molecular sieve, silica gel, calcium oxide, zeolite, activated carbon, and the like. Particularly, alkali metals for adsorbing and removing carbon dioxide gas include potassium hydroxide, sodium hydroxide, and the like. Lithium hydroxide or the like, or those obtained by encapsulating them with a polyolefin resin or the like can also be used.
【００３１】ゲッタ剤およびアルカリ金属は通常平均２
０〜３００μｍ程度の粒径とし、通気性のポリエチレン
製不織布、セルロース製不織布、ポリプロピレン製不織
布、ポリエチレンテレフタレート製不織布などに入れて
用いる。また、ガスバリア性の袋を封着する際には２０
〜１０ｍｍＨｇ程度まで排気した方がより好ましい。The getter agent and the alkali metal are usually 2 on average.
It has a particle size of about 0 to 300 μm, and is used in a breathable polyethylene nonwoven fabric, cellulose nonwoven fabric, polypropylene nonwoven fabric, polyethylene terephthalate nonwoven fabric, or the like. When sealing a gas barrier bag, 20
It is more preferable to evacuate to about 10 mmHg.
【００３２】本発明で密閉封着した独立気泡を有するペ
ンタフルオロヨウドエタン発泡剤の断熱パネルは、連続
構造の気泡を有する真空断熱パネルと大きく異なり、高
真空（１０~4〜１０~3Ｔｏｒｒ）にするための長時間排
気が必要なく、かつ、ガスバリア性の袋が破泡しても独
立構造の気泡中にペンタフルオロヨウドエタンが包括さ
れるため、断熱材の熱伝導率が異常に高くなる問題も解
決される。The insulation panel pentafluoro iodo ethane blowing agent having a closed sealed with closed cell in the present invention differs significantly from the vacuum insulation panels having a bubble continuous structure, high vacuum (10 ~ 4 ~10 ~ 3 Torr ) Pentafluoroiodoethane is included in the bubbles of the independent structure even if the gas barrier bag is ruptured, and the thermal conductivity of the heat insulating material becomes abnormally high. The problem is solved.
【００３３】こうした点から、ペンタフルオロヨウドエ
タンを発泡剤として用いた密閉封着型断熱パネルは、真
空断熱パネルのように高真空にしなくとも、優れた熱伝
導率の断熱材が達成できる。From these points, the hermetically sealed heat insulating panel using pentafluoroiodoethane as a foaming agent can achieve a heat insulating material having excellent thermal conductivity without applying a high vacuum unlike a vacuum heat insulating panel.
【００３４】一方、これまでのシクロペンタン発泡剤を
用いた硬質ポリウレタンフォームは飽和蒸気圧が低く、
気泡セル内の圧力低下によりフォーム強度の低下や収縮
が発生するため、高密度ウレタン材料を用いて壁内空間
に多量に充填する必要があった。On the other hand, rigid polyurethane foams using conventional cyclopentane blowing agents have low saturated vapor pressures,
Since the foam strength is reduced or shrunk due to the pressure drop in the cell, it is necessary to use a high-density urethane material to fill a large amount of the space in the wall.
【００３５】本発明では低密度・高流動性と高強度を両
立させるため、種々のポリオールと、シクロペンタンに
対する密度と圧縮強度の関係を調べた。その結果、密度
と圧縮強度は比例関係にあり、高密度になるほど高い圧
縮強度を示すことが分かった。In the present invention, the relationship between the density and the compressive strength of various polyols and cyclopentane was investigated in order to achieve both low density, high fluidity and high strength. As a result, it was found that the density and the compressive strength were in a proportional relationship, and the higher the density, the higher the compressive strength.
【００３６】また、冷凍冷蔵庫等の壁内空間に均一な断
熱パネルを形成するには、低密度・高流動性ウレタンの
方が、フォーム樹脂化やボイド発生が起こりにくい。こ
れは低密度で高流動性を有するためコア層部やスキン層
部にも樹脂化が発生しにくく、壁内の屈曲形状の影響も
受けにくいことから、気泡径分布も小さく均一フォーム
が形成されるものと考えられる。In order to form a uniform heat-insulating panel in a space in a wall of a refrigerator or the like, low-density and high-flow urethane is less liable to foam resin and generate voids. It has low density and high fluidity, so it is difficult for resin to occur in the core layer and skin layer, and it is hard to be affected by the bent shape in the wall. It is considered to be.
【００３７】さらに、低密度で高流動性および高強度の
硬質ポリウレタンフォームを得るには、シクロペンタン
と共に補助発泡剤である水の配合量も大きく影響する。
これまでの知見から、シクロペンタンと水の配合量を共
に多くすることにより、低密度化を容易に図ることがで
きることは知られていた。しかし、フォーム強度が大き
く低下することから、シクロペンタン配合量を減らし
て、熱伝導率に悪影響を及ぼす水配合量を逆に増やし、
気泡セル内の炭酸ガス分圧の向上を図ることで両立し
た。Further, in order to obtain a rigid polyurethane foam having a low density, a high fluidity and a high strength, the blending amount of water as an auxiliary blowing agent together with cyclopentane has a great influence.
From the findings so far, it has been known that the density can be easily reduced by increasing the amounts of cyclopentane and water. However, since the foam strength is greatly reduced, the amount of cyclopentane is reduced, and the amount of water that adversely affects the thermal conductivity is increased.
This was achieved by improving the partial pressure of carbon dioxide in the bubble cell.
【００３８】また、シクロペンタン発泡剤は従来発泡剤
と異なり、熱伝導率に対する水の悪影響が少なく、水１
重量部に対しシクロペンタン７重量部までの配合量が好
ましく、特に、３〜７重量部が好ましい。水配合量がこ
れよりも下回ると圧縮強度が劣り、水配合量が上回ると
熱伝導率が悪化する。一方、シクロペンタン配合量がこ
れよりも上回ると圧縮強度が低下する傾向がある。The cyclopentane blowing agent, unlike the conventional blowing agent, has little adverse effect on the thermal conductivity of water.
The blending amount is preferably up to 7 parts by weight of cyclopentane with respect to parts by weight, and particularly preferably 3 to 7 parts by weight. If the amount of water is lower than this, the compressive strength is inferior, and if the amount of water is higher, the thermal conductivity deteriorates. On the other hand, if the amount of cyclopentane exceeds the above range, the compressive strength tends to decrease.
【００３９】本発明ではシクロペンタンと水の混合発泡
剤を用いた低密度・高流動性の硬質ポリウレタンフォー
ムについては、コア層のフォーム密度を３１〜３４ｋｇ
／ｍ3（例えば、シクロペンタン：水＝７：１）にすれ
ば前記熱伝導率と圧縮強度の両特性の両立を図ることが
できる見通しを得た。In the present invention, for a low-density and high-flow rigid polyurethane foam using a mixed blowing agent of cyclopentane and water, the foam density of the core layer is 31 to 34 kg.
/ M 3 (for example, cyclopentane: water = 7: 1), it is expected that both the properties of the thermal conductivity and the compressive strength can be achieved.
【００４０】本発明に用いられるポリオールとしては、
ポリエーテルポリオールやポリエステルポリオールなど
がある。ポリエーテルポリオールは官能基数２〜８、水
酸基価３００〜６００ｍｇＫＯＨ／ｇの活性水素含有化
合物を開始剤とするポリオキシアルキレンポリオールが
挙げられる。The polyol used in the present invention includes:
Examples include polyether polyols and polyester polyols. Examples of the polyether polyol include a polyoxyalkylene polyol having an initiator containing an active hydrogen-containing compound having 2 to 8 functional groups and a hydroxyl value of 300 to 600 mgKOH / g.
【００４１】上記活性水素含有化合物としては、多価ア
ルコールおよび多価アミンなどが挙げられる。多価アル
コールとしては、プロピレングリコール、ジプロピレン
グリコールなどの２価アルコール、グリセリン、トリメ
チロールプロパンなどの３価アルコール、ジグリセリ
ン、メチルグルコシド、ソルビトール、ショ糖などの３
価以上の多価アルコールが挙げられる。Examples of the active hydrogen-containing compound include polyhydric alcohols and polyamines. Examples of polyhydric alcohols include dihydric alcohols such as propylene glycol and dipropylene glycol, trihydric alcohols such as glycerin and trimethylolpropane, and dihydric alcohols such as diglycerin, methyl glucoside, sorbitol, and sucrose.
And polyhydric alcohols having a valency or higher.
【００４２】多価アミンのアルキレンポリアミンとして
はエチレンジアミン、ジエチレントリアミンなど、アル
カノールアミンとしてはモノエタノールアミン、ジエタ
ノールアミン、トリエタノールアミン、イソプロパノー
ルアミンなど、芳香族多価アミンとしては２,４−トリ
レンジアミン、２,６−トリレンジアミン、２,３−トリ
レンジアミン、３,４−トリレンジアミンなどが、ま
た、ジアミノジフェニルメタン系、ビスフェノールＡ
系、ポリメチレンポリフェニルポリアミン系などが用い
られる。The polyalkylene alkylene polyamines include ethylenediamine and diethylenetriamine, the alkanolamines include monoethanolamine, diethanolamine, triethanolamine and isopropanolamine, and the aromatic polyamines include 2,4-tolylenediamine, , 6-tolylenediamine, 2,3-tolylenediamine, 3,4-tolylenediamine and the like, and diaminodiphenylmethane, bisphenol A
And polymethylene polyphenyl polyamines.
【００４３】ポリエステルポリオールとしては、官能基
数２〜４、水酸基価２５０〜５００ｍｇＫＯＨ／ｇの多
価アルコールと、多塩基酸の重縮合より得られるものが
挙げられる。多価アルコールとしては、エチレングリコ
ール、グリセリン、トリメチロールプロパンなど、糖類
としてはショ糖、ソルビトールなど、アルカノールアミ
ンとしてはジエタノールアミン、トリエタノールアミン
など、ポリアミンとしてはエチレンジアミン、トリレン
ジアミンなど、フェノールとしてはビスフェノールＡな
ど、多塩基酸としてはアジピン酸、フタル酸、多価カル
ボン酸などが用いられる。Examples of the polyester polyol include those obtained by polycondensation of a polyhydric alcohol having 2 to 4 functional groups and a hydroxyl value of 250 to 500 mgKOH / g with a polybasic acid. Polyhydric alcohols include ethylene glycol, glycerin, and trimethylolpropane; saccharides include sucrose and sorbitol; alkanolamines include diethanolamine and triethanolamine; polyamines include ethylenediamine and tolylenediamine; phenols include bisphenol Examples of polybasic acids such as A include adipic acid, phthalic acid, and polycarboxylic acids.
【００４４】また、反応触媒としては、例えば、テトラ
メチルヘキサメチレンジアミン、トリメチルアミノエチ
ルピペラジン、ペンタメチルジエチレントリアミン、ト
リエチレンジアミンなどの第３級アミン、および、トリ
メチルアミノエチルピペラジンの蟻酸塩、ジプロピレン
グリコール併用の遅効性触媒など、反応性が合致すれば
従来公知の触媒を使用することができる。Examples of the reaction catalyst include tertiary amines such as tetramethylhexamethylenediamine, trimethylaminoethylpiperazine, pentamethyldiethylenetriamine and triethylenediamine, and formate of trimethylaminoethylpiperazine and dipropylene glycol in combination. Conventionally known catalysts can be used as long as the reactivity matches, such as a slow-acting catalyst.
【００４５】反応触媒の配合量は、ポリオール成分１０
０重量部当り３〜５重量部が好ましい。The amount of the reaction catalyst is 10
3-5 parts by weight per 0 parts by weight is preferred.
【００４６】さらに、整泡剤は信越化学製のシリコーン
系発泡剤Ｘ−２０−１５４８、Ｘ−２０−１６１４、Ｘ
−２０−１６３４など、日本ユニカ製のＳＺ−１１２
７、ＳＺ−１６７１などが、プレミックス相溶性の安定
性からＳｉ分子量が１８００〜３０００およびＳｉ含有
率が２５〜３０の比較的低い乳化作用に適したものがよ
り好ましい。即ち、アルキレンオキサイド変性ポリジメ
チルシロキサンで末端にＯＨ基またはアルコキシ基を有
する有機シリコーン系化合物が使用できる。整泡剤の配
合量はポリオール成分１００重量部あたり１〜４重量部
が好ましい。Further, silicone foaming agents X-20-1548, X-20-1614, and X-20 manufactured by Shin-Etsu Chemical Co., Ltd.
SZ-112 manufactured by Nippon Unica, such as -20-1634
7, SZ-1671 and the like, more preferably those having a Si molecular weight of 1800 to 3000 and a Si content of 25 to 30 which are suitable for relatively low emulsifying action, from the stability of premix compatibility. That is, an organosilicone compound having an OH group or an alkoxy group at the end of an alkylene oxide-modified polydimethylsiloxane can be used. The amount of the foam stabilizer is preferably 1 to 4 parts by weight per 100 parts by weight of the polyol component.
【００４７】また、イソシアネートとしてはトリレンジ
イソシアネート（ＴＤＩ）およびジフェニルメタンジイ
ソシアネート（ＭＤＩ）などを用いる。ＴＤＩは異性体
の混合物、すなわち２,４−体１００％、２,４−体／
２,６−体が８０／２０、６５／３５（重量比）はもち
ろんこと、商品名三井コスモネートＴＲＣ、武田薬品の
タケネート４０４０など多官能性のタールを含有する粗
ＴＤＩも使用できる。As the isocyanate, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and the like are used. TDI is a mixture of isomers, that is, 2,4-isomer 100%, 2,4-isomer /
Crude TDI containing a multifunctional tar such as 2,6-body 80/20, 65/35 (weight ratio), as well as trade name Mitsui Cosmonate TRC and Takeda Pharmaceutical Takenate 4040 can be used.
【００４８】また、ＭＤＩとしては、４,４'−ジフェニ
ルメタンジイソシアネートを主成分とする純品の他に、
３核体以上の多角体を含有する商品名三井コスモネート
Ｍ−２００、武田薬品のミリオネートＭＲなどのポリメ
リックＭＤＩが使用できる。その他、ポリメチレンポリ
フェニルイソシアネート、１,６−ヘキサメチレンジイ
ソシアネートなどの芳香族系あるいは脂肪族系の多官能
イソシアネート、ウレタン変成トリレンジイソシアネー
ト、カルボジイミド変成ジフェニルメタンジイソシアネ
ートのイソシアネートなども使用することができる。As MDI, in addition to a pure product containing 4,4'-diphenylmethane diisocyanate as a main component,
Polymeric MDI such as Mitsui Cosmonate M-200, trade name containing three or more polyhedra, and Millionate MR of Takeda Pharmaceutical Co., Ltd. can be used. In addition, aromatic or aliphatic polyfunctional isocyanates such as polymethylene polyphenyl isocyanate and 1,6-hexamethylene diisocyanate, urethane-modified tolylene diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and the like can also be used.
【００４９】本発明の硬質ポリウレタンフォームを発泡
する条件としては、当業界で用いられている通常の発泡
機で形成され、例えば、プロマート社製ＰＵ−３０型発
泡機が用いられる。The conditions for foaming the rigid polyurethane foam of the present invention are those formed by a usual foaming machine used in the art, for example, PU-30 type foaming machine manufactured by Promart.
【００５０】発泡条件は発泡機の種類によって多少異な
るが通常は液温１８〜３０℃、吐出圧力８０〜１５０ｋ
ｇ／ｃｍ2、吐出量１５〜３０ｋｇ／ｍｉｎ、型箱の温
度は３５〜４５℃が好ましい。さらに好ましくは、液温
２０℃、吐出圧力１００ｋｇ／ｃｍ2、吐出量２５ｋｇ
／ｍｉｎ、型箱温度は４５℃程度がよい。The foaming conditions vary somewhat depending on the type of foaming machine, but usually the liquid temperature is 18 to 30 ° C. and the discharge pressure is 80 to 150 k.
g / cm 2 , the discharge rate is 15 to 30 kg / min, and the temperature of the mold box is preferably 35 to 45 ° C. More preferably, the liquid temperature is 20 ° C., the discharge pressure is 100 kg / cm 2 , and the discharge amount is 25 kg.
/ Min, and the mold box temperature is preferably about 45 ° C.
【００５１】このようにして、外箱と内箱からなる断熱
箱体の断熱壁を構成する断熱部材に、独立構造の気泡を
有し、熱伝導率が１３.５ｍＷ／ｍＫ以下の密閉封着型
断熱パネルと、シクロペンタン発泡剤を用いた低密度・
高流動性の硬質ポリウレタンフォームを組合わせた断熱
材構成としたことにより、地球環境に優しいシクロペン
タン発泡剤で、熱漏洩量低減による省エネ化および低密
度ウレタン使用による充填量低減が可能となり、低コス
ト化や歩留まり向上を図ることができる。従来の保冷装
置に匹敵するものを提供することが可能である。In this manner, the heat-insulating member constituting the heat-insulating wall of the heat-insulating box composed of the outer case and the inner case has a closed structure having air bubbles of an independent structure and a heat conductivity of 13.5 mW / mK or less. -Type insulation panel and low-density
The use of a heat-insulating material that combines a high-flowable rigid polyurethane foam makes it possible to save energy by reducing the amount of heat leakage and reduce the amount of filling by using low-density urethane. Costs and yields can be improved. It is possible to provide what is comparable to conventional refrigeration equipment.
【００５２】本発明を実施例並ぶに比較例を示して具体
的に説明する。なお、以下の実施例および比較例の中
で、部または％はそれぞれ重量部，重量％を表す。The present invention will be specifically described with reference to examples and comparative examples. In the following Examples and Comparative Examples, parts and% represent parts by weight and% by weight, respectively.
【００５３】〔実施例 １〕ペンタフルオロヨウドエタ
ン（ＰＦＥ）発泡剤を用いたポリオール成分としては、
平均水酸基価が４５０のプロピレンオキシド、およびエ
チレンオキシドで付加したトリレンジアミン系ポリエー
テルポリオール（ポリオールＡと称す）を５０部、平均
水酸基価が３５０のプロピレンオキシド、および、エチ
レンオキシドで付加したトリエタノールアミン系ポリエ
ーテルポリオール（ポリオールＢと称す）を２０部、平
均水酸基価が２５０のエチレンオキシドで付加したビス
フェノールＡ系ポリエーテルポリオール（ポリオールＣ
と称す）を１５部、平均水酸基価が４００のプロピレン
オキシドで付加したトリメチロールプロパン系ポリエー
テルポリオール（ポリオールＤと称す）を１０部、平均
水酸基価が３８０のエチレンオキシドで付加したトリレ
ンジアミン系ポリエステルポリオール（ポリオールＥと
称す）を５部の混合ポリオール成分１００部に、ＰＦＥ
発泡剤の配合量を５０部、水１.０部および反応触媒と
してトリメチルアミノエチルピペラジン１.２部とトリ
メチルアミノエチルピペラジン２部、トリエチレンジア
ミンのジプロピレングリコール液０.８部を配合した。Example 1 As a polyol component using a pentafluoroiodoethane (PFE) blowing agent,
50 parts of tolylenediamine polyether polyol (referred to as polyol A) added with propylene oxide and ethylene oxide having an average hydroxyl value of 450, and propylene oxide having an average hydroxyl value of 350 and triethanolamine added with ethylene oxide Bisphenol A-based polyether polyol (polyol C) obtained by adding 20 parts of polyether polyol (referred to as polyol B) with ethylene oxide having an average hydroxyl value of 250
Tolylenediamine-based polyester obtained by adding 15 parts of trimethylolpropane-based polyether polyol (referred to as polyol D) added with propylene oxide having an average hydroxyl value of 400 and ethylene oxide having an average hydroxyl value of 380. Polyol (referred to as polyol E) is mixed with 5 parts of a mixed polyol component (100 parts) and mixed with PFE.
50 parts of a foaming agent, 1.0 part of water, 1.2 parts of trimethylaminoethylpiperazine and 2 parts of trimethylaminoethylpiperazine as reaction catalyst, and 0.8 part of a dipropylene glycol liquid of triethylenediamine were mixed.
【００５４】また、整泡剤として有機シリコーン化合物
（Ｘ−２０−１５４８）２部、イソシアネート成分とし
てポリメチレンポリフェニルジイソシアネートを１２５
部を用いて、ガスバリア性の包袋中に発泡充填した。Further, 2 parts of an organic silicone compound (X-20-1548) as a foam stabilizer and 125 parts of polymethylene polyphenyl diisocyanate as an isocyanate component were used.
Using the part, foam filling was carried out in a gas barrier wrapper.
【００５５】ガスバリア性の包袋にはポリアクリロニト
リル素材を用いて、４８０ｍｍ×３５０ｍｍ×２５ｍｍ
ｔのフォーム形成を行い熱融着して、独立気泡を有する
硬質ポリウレタンフォームの密閉封着型断熱パネルを作
製した。[0055] A polyacrylonitrile material is used for the gas-barrier wrapper, and 480 mm x 350 mm x 25 mm
Form t was formed and heat-sealed to produce a hermetically sealed heat insulating panel of a rigid polyurethane foam having closed cells.
【００５６】上記断熱パネルの初期状態と室温で１ヶ月
経過後の平均温度０℃における熱伝導率について、熱流
計測定装置（英弘精機社製ＨＣ−０７３型）で評価した
結果を表１に示す。Table 1 shows the results of evaluation of the thermal conductivity at the average temperature of 0 ° C. after the lapse of one month at room temperature at the initial state of the heat insulating panel and at room temperature by a heat flow meter measuring device (HC-073 manufactured by Eiko Seiki Co., Ltd.). .
【００５７】[0057]
【表１】 [Table 1]
【００５８】表１から、初期状態の熱伝導率が１２.８
ｍＷ／ｍ・Ｋ、１ヶ月経過の熱伝導率が１３.０ｍＷ／
ｍ・Ｋを示し、経時変化が非常に小さいことが分かっ
た。From Table 1, it can be seen that the thermal conductivity in the initial state is 12.8.
mW / m · K, thermal conductivity after 1 month is 13.0mW /
m · K, indicating that the change with time was very small.
【００５９】次に、上記で得た密閉封着型断熱パネル
を、冷凍冷蔵庫の断熱材に用いた実施例並びに比較例に
ついて、図面を参照しながら以下説明する。Next, examples and comparative examples in which the hermetically sealed heat insulating panel obtained above was used as a heat insulating material for a refrigerator-freezer will be described below with reference to the drawings.
【００６０】図１は、冷凍冷蔵庫の全体模式斜視図を示
す。また、図２は、ＰＦＥ発泡剤を用いた密閉封着型断
熱パネル４を断熱箱体１中に挿入した模式斜視図を示
す。また、図３は、断熱パネルを壁内空間に挿入した細
部の平面模式断面図を示す。さらに、図４には、断熱箱
体１中にシクロペンタン発泡剤の硬質ポリウレタンフォ
ーム６を４点注入で充填する状態、並びに、フォームの
コア層密度および圧縮強度を評価する測定サンプル１１
の模式斜視図を示す。FIG. 1 is an overall schematic perspective view of a refrigerator-freezer. FIG. 2 is a schematic perspective view in which a hermetically sealed heat insulating panel 4 using a PFE foaming agent is inserted into the heat insulating box 1. FIG. 3 is a schematic plan cross-sectional view of a detail in which the heat insulating panel is inserted into the space in the wall. Further, FIG. 4 shows a state in which the rigid polyurethane foam 6 of the cyclopentane foaming agent is filled into the heat insulating box 1 by four-point injection, and a measurement sample 11 for evaluating the core layer density and compressive strength of the foam.
1 shows a schematic perspective view of FIG.
【００６１】即ち、鉄製の外箱２と汎用ＡＢＳ樹脂の内
箱３との隙間部分の外箱鉄板内面側に、ＰＦＥ発泡剤の
密閉封着型断熱パネルを接着剤５などで固定し、さら
に、空隙部分にシクロペンタン発泡剤の硬質ポリウレタ
ンフォーム６を発泡充填して構成した冷凍冷蔵庫であ
る。That is, a hermetically sealed heat insulating panel made of a PFE foaming agent is fixed to the inner surface of the outer box iron plate at the gap between the outer box 2 made of iron and the inner box 3 made of general-purpose ABS resin with an adhesive 5 or the like. This is a refrigerator-freezer constructed by foam-filling a rigid polyurethane foam 6 of a cyclopentane foaming agent in a void portion.
【００６２】ここで、密閉封着型断熱パネル４は、冷凍
冷蔵庫の左右各２枚に無溶剤アクリルエマルジョンなど
の接着剤５を刷毛、または、スプレーガンなどで均一に
塗布し外箱２の内面側に固定した後、内箱３と組み立て
発泡前の箱体を作製した。Here, the hermetically sealed heat insulating panel 4 is formed by uniformly applying an adhesive 5 such as a solvent-free acrylic emulsion to each of the left and right sheets of the refrigerator and refrigerator with a brush or a spray gun or the like. After fixing to the side, the inner box 3 and the box body before assembling and foaming were produced.
【００６３】その後、ウレタンフォーム発泡雇い治具に
発泡前の箱体をセット後、予備加熱を行って、シクロペ
ンタン発泡剤のポリオール成分には平均水酸基価が４０
０のプロピレンオキシドおよびエチレンオキシドで付加
したトリレンジアミン系ポリエーテルポリオール（ポリ
オールＦと称す）を５０部、平均水酸基価が３８０のプ
ロピレンオキシドおよびエチレンオキシドで付加したト
リエタノールアミン系ポリエーテルポリオール（ポリオ
ールＧと称す）を１５部、平均水酸基価が２８０のエチ
レンオキシドで付加したビスフェノールＡ系ポリエーテ
ルポリオール（ポリオールＨと称す）を２０部、平均水
酸基価が４２０のプロピレンオキシドで付加したシュー
クローズ系ポリエーテルポリオール（ポリオールＩと称
す）を１０部、平均水酸基価が４７０のプロピレンオキ
シドで付加したグリセリン系ポリエーテルポリオール
（ポリオールＪと称す）を５部の混合ポリオールを調製
した。Then, after setting the box before foaming in the urethane foam foaming jig, preheating is performed, and the polyol component of the cyclopentane foaming agent has an average hydroxyl value of 40%.
50 parts of tolylenediamine-based polyether polyol (referred to as polyol F) added with propylene oxide and ethylene oxide of 0, and triethanolamine-based polyether polyol (added with polyol G) added with propylene oxide and ethylene oxide having an average hydroxyl value of 380. 15 parts, bisphenol A-based polyether polyol (referred to as polyol H) added with ethylene oxide having an average hydroxyl value of 280 (20 parts), and shoe-closed polyether polyol (added with propylene oxide having an average hydroxyl value of 420) ( A mixed polyol was prepared by mixing 10 parts of polyol I) and 5 parts of a glycerin-based polyether polyol (referred to as polyol J) added with propylene oxide having an average hydroxyl value of 470.
【００６４】上記の混合ポリオール１００部に対しシク
ロペンタン発泡剤を１３部、水２.０部および反応触媒
としてトリメチルアミノエチルピペラジン１.６部とト
リメチルアミノエチルピペラジン２.４部、トリエチレ
ンジアミンのジプロピレングリコール液０.４部、整泡
剤として有機シリコーン化合物（Ｘ−２０−１６１４）
２部、イソシアネート成分としてポリメチレンポリフェ
ニルジイソシアネートを１３２部使用した硬質ポリウレ
タンフォームを空隙部分に発泡充填する。13 parts of cyclopentane blowing agent, 2.0 parts of water, 1.6 parts of trimethylaminoethylpiperazine and 2.4 parts of trimethylaminoethylpiperazine as reaction catalyst, 2.4 parts of trimethylaminoethylpiperazine, diethylenediamine 0.4 parts of a propylene glycol solution, an organic silicone compound (X-20-1614) as a foam stabilizer
2 parts, a rigid polyurethane foam using 132 parts of polymethylene polyphenyl diisocyanate as an isocyanate component is foam-filled in the void portion.
【００６５】その時、ウレタンフォームのポリオールと
イソシアネートが化学反応し発泡圧力の加圧により、発
泡ウレタンフォームが冷凍冷蔵庫の壁内空間に注入充填
されて、ＰＦＥ発泡剤の密閉封着型断熱パネルが挿入さ
れた断熱箱体が形成される。注入時温度は約４５℃、ポ
リオールおよびイソシアネートの液温は約２０℃で行っ
た。At this time, the polyol of the urethane foam and the isocyanate undergo a chemical reaction, and the foaming pressure is increased, whereby the foamed urethane foam is injected and filled into the space in the wall of the refrigerator, and the hermetically sealed heat insulating panel of the PFE foaming agent is inserted. A heat-insulated box is formed. The injection was performed at a temperature of about 45 ° C., and the liquid temperatures of the polyol and isocyanate were about 20 ° C.
【００６６】これにより、密閉封着型断熱パネルが硬質
ポリウレタンフォームで完全に覆われた形で、断熱箱体
１からなる冷凍冷蔵庫を作製した。その際、ウレタン材
料のゼロパック（実機充填に必要な最低注入量）を設定
した後、パック率１１０％で注入した冷凍冷蔵庫の箱体
について、ウレタン注入口から少なくとも５００ｍｍ以
上離れた断熱材部分からフォームサンプルを採取し、コ
ア層密度については２００ｍｍ×２００ｍｍ×２０ｍｍ
ｔのサンプルの寸法と重量を測定後、重量を体積で除し
た値で評価した。As a result, a refrigerator-freezer comprising the heat-insulating box 1 was produced with the hermetically sealed heat-insulating panel completely covered with the rigid polyurethane foam. At that time, after setting a zero pack of urethane material (minimum injection amount required for filling in the actual machine), the freezing refrigerator box injected at a pack rate of 110% was separated from the heat insulating material portion at least 500 mm or more away from the urethane injection port. A foam sample is collected and the core layer density is 200 mm × 200 mm × 20 mm
After measuring the size and weight of the sample at t, the weight was divided by the volume and evaluated.
【００６７】また、圧縮強度は５０ｍｍ×５０ｍｍ×２
０ｍｍｔのフォームサンプルを送り速度４ｍｍ／ｍｉｎ
で負荷し、１０％変形時の荷重を元の受圧面積で除した
値で評価した。これらの結果を表１に併せて示す。The compression strength is 50 mm × 50 mm × 2.
0mmt foam sample feed rate 4mm / min
And evaluated by a value obtained by dividing the load at the time of 10% deformation by the original pressure receiving area. The results are shown in Table 1.
【００６８】表１から、コア層密度が３２ｋｇ／ｍ3と
低密度で、圧縮強度も０.１５ＭＰａと高い値を示し
た。From Table 1, the core layer density was as low as 32 kg / m 3 and the compressive strength was as high as 0.15 MPa.
【００６９】さらに、シクロペンタン（ＣＰ）発泡剤の
ポリウレタン材料を用いて、キャビネット壁内空間の内
容積が約１８０リットルの冷凍冷蔵庫について、パック
率１１０％時のウレタン実充填量も調べた。その結果、
充填量が５.４５ｋｇまで低減が可能となり、従来の高
密度硬質ポリウレタンフォームに比べ約１２〜１５％の
ウレタン材料が節約できることを確認した。Further, using a polyurethane material of a cyclopentane (CP) foaming agent, the actual filling amount of urethane at a pack ratio of 110% was examined for a refrigerator having an inner volume of about 180 liters in the cabinet wall. as a result,
It has been confirmed that the filling amount can be reduced to 5.45 kg, and about 12 to 15% of urethane material can be saved as compared with the conventional high-density rigid polyurethane foam.
【００７０】また、密閉封着型断熱パネル４を挿入した
硬質ポリウレタンフォームの発泡充填を行なって断熱箱
体１を形成した冷凍冷蔵庫に、冷凍サイクル部品（圧縮
機／コンデンサ／エバポレータ）を組み込んで測定した
結果、熱漏洩量が約６〜１０％低減し、消費電力量も約
２〜３Ｋｗｈ／月の省エネ化が達成された。Further, a refrigerating cycle component (compressor / condenser / evaporator) is installed in a refrigerator having a heat insulating box 1 formed by foaming and filling a rigid polyurethane foam into which a hermetically sealed heat insulating panel 4 is inserted. As a result, the amount of heat leakage was reduced by about 6 to 10%, and the energy consumption was also reduced by about 2 to 3 Kwh / month.
【００７１】また、ＰＦＥ発泡剤は、ガスバリア性の包
袋中に密閉されているため、内箱材の汎用ＡＢＳ樹脂に
よるケミカルアタックも起こらず、発泡剤使用量の低
減、または、単品発泡剤を用いることにより再生も可能
となる。さらには、密閉封着型断熱パネルとすることに
より、真空断熱パネルのように高減圧化にする必要も無
く、フィルムのピンホール化による熱伝導率上昇も発生
しないことが分かった。Since the PFE foaming agent is hermetically sealed in a gas-barrier wrapper, no chemical attack is caused by the general-purpose ABS resin of the inner box material, so that the amount of the foaming agent used can be reduced or a single foaming agent can be used. By using it, reproduction is also possible. Further, it was found that the use of the hermetically sealed heat insulating panel did not require a high pressure reduction unlike the vacuum heat insulating panel, and did not cause an increase in thermal conductivity due to the formation of pinholes in the film.
【００７２】〔実施例 ２〕表１に示すポリオールＡ〜
ＥポリオールとＰＦＥ発泡剤を５０部、水１.０部およ
び反応触媒、整泡剤、イソシアネートを用いて４８０ｍ
ｍ×３５０ｍｍ×２５ｍｍｔのウレタンフォームを作製
後、パネルサイズとして４００ｍｍ×３００ｍｍ×２０
ｍｍｔに切断してコア層フォームを形成した。Example 2 Polyols A to A shown in Table 1
480 m using 50 parts of E polyol and PFE foaming agent, 1.0 part of water, a reaction catalyst, a foam stabilizer, and isocyanate
After preparing urethane foam of mx 350 mm x 25 mmt, the panel size was 400 mm x 300 mm x 20
mmt to form a core layer foam.
【００７３】これをガスバリア性のポリエチレンフィル
ム包袋に挿入して、ポリエチレン製不織布に包装した水
酸化カリウム１５ｇを一緒に入れ、約２０ｍｍＨｇ程に
排気しながら熱融着を行い、密閉封着型断熱パネルを作
製し、表１に示す熱伝導率を評価した。表１から、初期
の熱伝導率１２.６ｍＷ／ｍＫに比べ１ヶ月経過後の熱
伝導率は１２.２ｍＷ／ｍＫまで低減することが分かっ
た。This was inserted into a polyethylene film wrapping bag having gas barrier properties, and 15 g of potassium hydroxide wrapped in a polyethylene non-woven fabric was put together, and heat fusion was carried out while evacuating to about 20 mmHg to obtain a hermetically sealed heat insulating material. A panel was prepared, and the thermal conductivity shown in Table 1 was evaluated. From Table 1, it was found that the thermal conductivity after one month had passed was reduced to 12.2 mW / mK compared to the initial thermal conductivity of 12.6 mW / mK.
【００７４】さらに、密閉封着型断熱パネルを装着し
て、表１のポリオールＦ〜Ｊとシクロペンタン発泡剤を
１４部と水２.１部を混入した硬質ポリウレタンフォー
ムの発泡充填を行い、冷凍冷蔵庫の箱体を作製した。表
１にコア層密度と圧縮強度を示す。表１から、コア層密
度が３１.５ｋｇ／ｍ3と低密度になり、圧縮強度も０.
１４ＭＰａと高い値を示すものが得られた。Further, a hermetically sealed heat insulating panel was attached, and a rigid polyurethane foam containing 14 parts of polyols F to J of Table 1 and cyclopentane blowing agent mixed with 2.1 parts of water was foam-filled, followed by freezing. A refrigerator box was made. Table 1 shows the core layer density and the compressive strength. From Table 1, the core layer density was as low as 31.5 kg / m 3 , and the compressive strength was also at 0.
A high value of 14 MPa was obtained.
【００７５】さらに、キャビネット壁内空間の内容積が
約１８０リットルの冷凍冷蔵庫について、パック率１１
０％時のウレタン実充填量を調べた結果、充填量が５.
３５ｋｇまで低減可能となり、高密度の硬質ポリウレタ
ンフォームに比べ約１２〜１５％のウレタン材料が節約
できた。Further, for a refrigerator having a cabinet wall having an inner volume of about 180 liters, a pack rate of 11
As a result of examining the actual filling amount of urethane at 0%, the filling amount was 5.
The weight can be reduced to 35 kg, and about 12 to 15% of the urethane material can be saved as compared with the high-density rigid polyurethane foam.
【００７６】また、密閉封着型断熱パネルを挿入した硬
質ポリウレタンフォームを発泡充填した断熱箱体を形成
した冷凍冷蔵庫に、冷凍サイクル部品（圧縮機／コンデ
ンサ／エバポレータ）を組み込んで測定した結果、熱漏
洩量が約６〜１０％低減し、消費電力量も約２〜３Ｋｗ
ｈ／月の省エネ化が達成された。Further, as a result of incorporating a refrigeration cycle component (compressor / condenser / evaporator) into a refrigerator having a heat-insulating box formed by foam-filling a rigid polyurethane foam with a hermetically sealed heat-insulating panel inserted therein, the heat was measured. The leakage amount is reduced by about 6-10%, and the power consumption is also about 2-3Kw
h / month energy saving was achieved.
【００７７】〔実施例 ３〕表１に示すポリオールＡ〜
ＥとＰＦＥ発泡剤を５５部、水０.５部と反応触媒、整
泡剤、イソシアネートを用いてガスバリア性のポリエチ
レンテレフタレートフィルム包袋のアルミパネルに、４
８０ｍｍ×３５０ｍｍ×２５ｍｍｔのパネルを発泡充填
後、ポリエチレンテレフタレート製不織布に包装したモ
レキューラシーブス１５ｇを一緒に入れ、熱融着を行っ
て密閉封着型断熱パネルを作製し、熱伝導率を評価し
た。Example 3 Polyols A to A shown in Table 1
E and PFE foaming agent 55 parts, water 0.5 part, reaction catalyst, foam stabilizer, isocyanate using gas barrier polyethylene terephthalate film on aluminum panel
After foam-filling a panel of 80 mm x 350 mm x 25 mmt, 15 g of molecular sieves packed in a non-woven fabric made of polyethylene terephthalate are put together, heat-sealed to produce a hermetically sealed heat insulating panel, and the thermal conductivity is evaluated. did.
【００７８】表１から、初期値と１ヶ月経過後の熱伝導
率は１２.５ｍＷ／ｍＫと１２.６ｍＷ／ｍＫでほとんど
変わらず、経時変化が非常に小さいことが分かった。From Table 1, it was found that the initial value and the thermal conductivity after one month passed were hardly changed between 12.5 mW / mK and 12.6 mW / mK, and the change with time was very small.
【００７９】さらに、密閉封着型断熱パネルを装着して
表１のポリオールＦ〜Ｊとシクロペンタン発泡剤を１２
部と水２.２部を混入し、硬質ポリウレタンフォームの
発泡充填を行い冷凍冷蔵庫の箱体を作製した。表１にコ
ア層密度と圧縮強度を示す。Further, a hermetically sealed heat insulating panel was attached, and the polyols F to J and the cyclopentane blowing agent shown in Table 1 were mixed in 12 parts.
The mixture was mixed with 2.2 parts of water and 2.2 parts of water, and foamed and filled with a rigid polyurethane foam to prepare a refrigerator-freezer box. Table 1 shows the core layer density and the compressive strength.
【００８０】表１から、コア層密度が３３.５ｋｇ／ｍ3
と低密度になり、圧縮強度も０.１７ＭＰａと高い値の
ものが得られた。As shown in Table 1, the core layer density was 33.5 kg / m 3.
And the compression strength was as high as 0.17 MPa.
【００８１】さらに、キャビネット空間部分の内容積が
約１８０リットルの冷凍冷蔵庫について、パック率１１
０％のウレタン実充填量を調べた結果、５.５０ｋｇま
で低減可能となり、高密度のフォームに比べ約１２〜１
５％のウレタン材料が節約できた。Further, for a refrigerator having a cabinet space of about 180 liters in inner volume, a pack rate of 11
As a result of examining the actual filling amount of urethane of 0%, the urethane can be reduced to 5.50 kg, which is about 12 to 1 compared with the high density foam.
5% urethane material was saved.
【００８２】また、密閉封着型断熱パネルを挿入した硬
質ポリウレタンフォームを発泡充填した断熱箱体で形成
した冷凍冷蔵庫に、冷凍サイクル部品（圧縮機／コンデ
ンサ／エバポレータ）を組み込んで測定した結果、熱漏
洩量が約６〜１０％低減し、消費電力量も約２〜３Ｋｗ
ｈ／月の省エネ化が達成された。Further, as a result of incorporating a refrigeration cycle component (compressor / condenser / evaporator) into a refrigerator-freezer formed of a heat-insulated box foam-filled with a rigid polyurethane foam into which a hermetically sealed heat-insulating panel is inserted, the heat was measured. The leakage amount is reduced by about 6-10%, and the power consumption is also about 2-3Kw
h / month energy saving was achieved.
【００８３】〔実施例 ４〕表１に示すポリオールＡ〜
ＥとＰＦＥ発泡剤を５５部、水１.５部および反応触
媒、整泡剤、イソシアネートを用いて、４８０ｍｍ×３
５０ｍｍ×２５ｍｍｔのフォームを形成後、パネルサイ
ズを４００ｍｍ×３００ｍｍ×１５ｍｍｔに切断したコ
ア層フォームを取出し後、ガスバリア性のポリアクリロ
ニトリルフィルム包袋に挿入し、ポリエチレン製不織布
に包装したモレキュラーシーブス１０ｇと活性炭５ｇを
約１０ｍｍＨｇに排気しながら熱融着を行い、密閉封着
型断熱パネルを作製し、熱伝導率を評価した。Example 4 Polyols A to A shown in Table 1
480 mm × 3 using 55 parts of E and PFE foaming agent, 1.5 parts of water, a reaction catalyst, a foam stabilizer, and isocyanate
After forming a foam of 50 mm × 25 mmt, take out the core layer foam cut into a panel size of 400 mm × 300 mm × 15 mmt, insert it into a gas-barrier polyacrylonitrile film bag, and package 10 g of molecular sieves packed in a nonwoven fabric made of polyethylene and activated carbon. Heat fusion was performed while exhausting 5 g to about 10 mmHg to produce a hermetically sealed heat insulating panel, and the thermal conductivity was evaluated.
【００８４】表１から、初期値と１ヶ月経過後の熱伝導
率は１２.４ｍＷ／ｍＫと１２.５ｍＷ／ｍＫでほとんど
変わらず、経時変化が非常に小さいことが分かった。From Table 1, it was found that the initial value and the thermal conductivity after one month passed were hardly changed between 12.4 mW / mK and 12.5 mW / mK, and the change with time was very small.
【００８５】さらに、密閉封着型断熱パネルを装着して
表１のポリオールＦ〜Ｊとシクロペンタン発泡剤を１１
部と水２.４部を混入し、硬質ポリウレタンフォームの
発泡充填を行い冷凍冷蔵庫の箱体を作製した。表１にコ
ア層密度と圧縮強度を示す。Further, a hermetically sealed heat insulating panel was attached, and the polyols F to J and cyclopentane blowing agent shown in
The mixture was mixed with 2.4 parts of water and filled with rigid polyurethane foam by foaming to produce a refrigerator-freezer box. Table 1 shows the core layer density and the compressive strength.
【００８６】表１から、コア層密度が３２.９ｋｇ／ｍ3
と低密度になり、圧縮強度も０.１８ＭＰａと高い値の
ものが得られた。As shown in Table 1, the core layer density was 32.9 kg / m 3.
, And a high compression strength of 0.18 MPa was obtained.
【００８７】さらに、キャビネット壁内空間の内容積が
約１８０リットルの冷凍冷蔵庫について、パック率１１
０％時のウレタン実充填量を調べた結果、充填量が５.
３８ｋｇまで低減可能となり、高密度の硬質ポリウレタ
ンフォームに比べ約１２〜１５％のウレタン材料が節約
できた。Further, for a refrigerator having a cabinet wall having an inner volume of about 180 liters, a pack rate of 11
As a result of examining the actual filling amount of urethane at 0%, the filling amount was 5.
The weight can be reduced to 38 kg, and about 12 to 15% of the urethane material can be saved as compared with the high-density rigid polyurethane foam.
【００８８】また、密閉封着型断熱パネルを挿入した硬
質ポリウレタンフォームを発泡充填した断熱箱体で形成
した冷凍冷蔵庫に、冷凍サイクル部品（圧縮機／コンデ
ンサ／エバポレータ）を組み込んで測定した結果、熱漏
洩量が約６〜１０％低減し、消費電力量も約２〜３Ｋｗ
ｈ／月の省エネ化が達成された。Further, as a result of incorporating a refrigeration cycle component (compressor / condenser / evaporator) into a refrigerator-freezer formed of a heat-insulated box foam-filled with a rigid polyurethane foam into which a hermetically sealed heat-insulating panel is inserted, the result was measured. The leakage amount is reduced by about 6-10%, and the power consumption is also about 2-3Kw
h / month energy saving was achieved.
【００８９】〔実施例 ５〕表１に示すポリオールＡ〜
ＥとＰＦＥ発泡剤を４５部、水１.０部および反応触
媒、整泡剤、イソシアネートを用いて、ガスバリア性の
ポリプロピレンフィルム包袋のアルミパネルに、サイズ
が４８０ｍｍ×３５０ｍｍ×２５ｍｍｔのパネルを発泡
充填後、ポリプロピレン製不織布で包装したポリオレフ
ィンでカプセル化した水酸化ナトリウム２０ｇを一緒に
熱融着を行い、密閉封着型断熱パネルを作製し、熱伝導
率を評価した。Example 5 Polyols A to A shown in Table 1
Using E and PFE foaming agents of 45 parts, water of 1.0 parts, a reaction catalyst, a foam stabilizer and an isocyanate, foam a panel of 480 mm × 350 mm × 25 mmt on an aluminum panel of a polypropylene film bag with gas barrier properties. After filling, 20 g of sodium hydroxide encapsulated with polyolefin wrapped with a polypropylene nonwoven fabric was heat-sealed together to produce a hermetically sealed heat insulating panel, and the thermal conductivity was evaluated.
【００９０】表１から、１ヶ月経過後の熱伝導率は１
１.８ｍＷ／ｍＫを示し初期の熱伝導率１２.２ｍＷ／ｍ
Ｋよりも逆に熱伝導率が低減された。From Table 1, the thermal conductivity after one month has passed is 1
It shows 1.8 mW / mK and the initial thermal conductivity is 12.2 mW / m
Conversely, the thermal conductivity was lower than that of K.
【００９１】さらに、密閉封着型断熱パネルを装着して
表１のポリオールＦ〜Ｊとシクロペンタン発泡剤を１２
部と水２.５部を混入し、硬質ポリウレタンフォームを
発泡充填し、冷凍冷蔵庫の箱体を作製した。表１にコア
層密度と圧縮強度を示す。Further, a hermetically sealed heat insulating panel was mounted, and polyols F to J and cyclopentane blowing agent shown in Table 1 were added to 12
The mixture was mixed with 2.5 parts of water and 2.5 parts of water, and foamed and filled with a rigid polyurethane foam to prepare a refrigerator-freezer box. Table 1 shows the core layer density and the compressive strength.
【００９２】表１から、コア層密度が３２.８ｋｇ／ｍ3
と低密度になり、圧縮強度も０.１９ＭＰａと高い値を
示した。さらに、キャビネット壁内空間の内容積が約１
８０リットルの冷凍冷蔵庫について、パック率１１０％
時のウレタン実充填量を調べた結果、充填量が５.４０
ｋｇまで低減が可能となり高密度の硬質ポリウレタンフ
ォームに比べ約１２〜１５％のウレタン材料が節約でき
た。From Table 1, the core layer density was 32.8 kg / m 3.
And the compressive strength showed a high value of 0.19 MPa. Furthermore, the internal volume of the space inside the cabinet wall is about 1
110% pack rate for 80-liter freezer refrigerator
As a result of examining the actual filling amount of urethane at the time, the filling amount was 5.40.
kg, which saves about 12 to 15% of urethane material compared to high-density rigid polyurethane foam.
【００９３】また、密閉封着型断熱パネルを挿入した硬
質ポリウレタンフォームを発泡充填した断熱箱体を形成
した冷凍冷蔵庫に、冷凍サイクル部品（圧縮機／コンデ
ンサ／エバポレータ）を組み込んで測定した結果、熱漏
洩量が約６〜１０％低減し、消費電力量も約２〜３Ｋｗ
ｈ／月の省エネ化が達成された。Further, as a result of incorporating a refrigeration cycle component (compressor / condenser / evaporator) into a refrigerator-freezer having a heat-insulating box formed by foam-filling a rigid polyurethane foam into which a hermetically sealed heat-insulating panel is inserted, the heat was measured. The leakage amount is reduced by about 6-10%, and the power consumption is also about 2-3Kw
h / month energy saving was achieved.
【００９４】〔実施例 ６〕表１に示すポリオールＡ〜
ＥとＰＦＥ発泡剤を４０部、水０.５部および反応触
媒、整泡剤、イソシアネートを用いて、ガスバリア性の
ポリプロピレンフィルム包袋のアルミパネルに、サイズ
が４８０ｍｍ×３５０ｍｍ×２５ｍｍｔのパネルを発泡
充填後、セルロース製の不織布に包装した水酸化ナトリ
ウム１５ｇを一緒に熱融着を行って、密閉封着型断熱パ
ネルを作製し熱伝導率を評価した。Example 6 Polyols A to A shown in Table 1
Using 480 parts of E and PFE foaming agent, 0.5 part of water, a reaction catalyst, a foam stabilizer and an isocyanate, foam a panel of 480 mm x 350 mm x 25 mmt on an aluminum panel of a polypropylene film bag with gas barrier properties. After filling, 15 g of sodium hydroxide packaged in a nonwoven fabric made of cellulose was heat-sealed together to produce a hermetically sealed heat insulating panel, and the thermal conductivity was evaluated.
【００９５】表１から、１ヶ月経過の熱伝導率は１１.
６ｍＷ／ｍＫで、初期の熱伝導率１２.２ｍＷ／ｍＫよ
りも低減される。From Table 1, the thermal conductivity after one month was 11.
At 6 mW / mK, it is reduced from the initial thermal conductivity of 12.2 mW / mK.
【００９６】さらに、密閉封着型断熱パネルを装着して
表１のポリオールＦ〜Ｊとシクロペンタン発泡剤を１１
部と水２.０部を混入し、硬質ポリウレタンフォームの
発泡充填を行い、冷凍冷蔵庫の箱体を作製し、コア層密
度と圧縮強度を測定した。Further, a hermetically sealed heat insulating panel was attached, and the polyols F to J and the cyclopentane blowing agent shown in
Of water and 2.0 parts of water, and foamed and filled with a rigid polyurethane foam to prepare a refrigerator-freezer box. The core layer density and the compressive strength were measured.
【００９７】表１から、コア層密度が３３.７ｋｇ／ｍ3
と低密度になり、圧縮強度も０.１６ＭＰａと高い値の
ものを得た。From Table 1, the core layer density was 33.7 kg / m 3.
And the compression strength was as high as 0.16 MPa.
【００９８】さらに、キャビネット壁内空間の内容積が
約１８０リットルの冷凍冷蔵庫について、パック率１１
０％時のウレタン実充填量を調べた結果、充填量が５.
４５ｋｇまで低減が可能となり、高密度の硬質ポリウレ
タンフォームに比べ約１２〜１５％のウレタン材料が節
約できた。Further, for a refrigerator having a cabinet wall having an inner volume of about 180 liters, a pack rate of 11
As a result of examining the actual filling amount of urethane at 0%, the filling amount was 5.
The weight can be reduced to 45 kg, and about 12 to 15% of the urethane material can be saved as compared with the high-density rigid polyurethane foam.
【００９９】また、密閉封着型断熱パネルを挿入した硬
質ポリウレタンフォームを発泡充填し断熱箱体を形成し
た冷凍冷蔵庫に、冷凍サイクル部品（圧縮機／コンデン
サ／エバポレータ）を組み込んで測定した結果、熱漏洩
量が約６〜１０％低減し、消費電力量も約２〜３Ｋｗｈ
／月の省エネ化が達成された。Further, as a result of incorporating a refrigeration cycle component (compressor / condenser / evaporator) into a refrigerator having a heat-insulating box formed by foam-filling a rigid polyurethane foam into which a hermetically sealed heat insulating panel is inserted, the heat was measured. The leakage amount is reduced by about 6-10%, and the power consumption is also about 2-3Kwh
/ Month energy saving.
【０１００】〔実施例 ７〕表１に示すポリオールＡ〜
ＥとＰＦＥ発泡剤を４５部、水１.５部および反応触
媒、整泡剤、イソシアネートを用いて、ガスバリア性の
ポリプロピレンフィルム包袋のアルミパネルとして、サ
イズが４８０ｍｍ×３５０ｍｍ×２５ｍｍｔのパネルを
発泡充填後、ポリプロピレン製の不織布で包装した水酸
化ナトリウム２０ｇを一緒に熱融着を行って、密閉封着
型断熱パネルを作製し、熱伝導率を評価した。Example 7 Polyols A to A shown in Table 1
E and PFE foaming agent, 45 parts, water 1.5 parts, reaction catalyst, foam stabilizer, isocyanate, foamed panel of size 480mm x 350mm x 25mmt as aluminum panel of gas barrier polypropylene film bag. After filling, 20 g of sodium hydroxide packaged with a nonwoven fabric made of polypropylene was heat-sealed together to produce a hermetically sealed heat insulating panel, and the thermal conductivity was evaluated.
【０１０１】表１から明らかなように、１ヶ月経過後の
熱伝導率は１２.０ｍＷ／ｍＫで、初期の熱伝導率１２.
６ｍＷ／ｍＫよりも低減された。As is clear from Table 1, the thermal conductivity after one month was 12.0 mW / mK, and the initial thermal conductivity was 12.
It was reduced below 6 mW / mK.
【０１０２】さらに、密閉封着型断熱パネルを内箱のＡ
ＢＳ樹脂側に装着して表１のポリオールＦ〜Ｊとシクロ
ペンタン発泡剤を１３部と水２.０部を混入し、硬質ポ
リウレタンフォームの発泡充填を行い、冷凍冷蔵庫の箱
体を作製しコア層密度と圧縮強度を測定した。Further, the hermetically sealed heat insulating panel is attached to the inner box A
Attached to the BS resin side, 13 parts of polyols F to J of Table 1 and cyclopentane foaming agent were mixed with 13 parts of water and 2.0 parts of water, foamed and filled with a hard polyurethane foam, and a box of a refrigerator was prepared. The bed density and compressive strength were measured.
【０１０３】表１から、コア層密度が３２.５ｋｇ／ｍ3
と低密度になり、圧縮強度も０.１５ＭＰａと高い値の
ものを得た。From Table 1, the core layer density was 32.5 kg / m 3.
And the compression strength was as high as 0.15 MPa.
【０１０４】さらに、キャビネット壁内空間の内容積が
約１８０リットルの冷凍冷蔵庫について、パック率１１
０％時のウレタン実充填量を調べた結果、充填量が５.
４７ｋｇまで低減が可能となり、高密度の硬質ポリウレ
タンフォームに比べ約１２〜１５％のウレタン材料が節
約できた。Further, for a refrigerator having a cabinet wall having an inner volume of about 180 liters, a pack rate of 11
As a result of examining the actual filling amount of urethane at 0%, the filling amount was 5.
The weight can be reduced to 47 kg, and about 12 to 15% of the urethane material can be saved as compared with the high-density rigid polyurethane foam.
【０１０５】また、密閉封着型断熱パネルを挿入した硬
質ポリウレタンフォームを発泡充填し断熱箱体を形成し
た冷凍冷蔵庫に、冷凍サイクル部品（圧縮機／コンデン
サ／エバポレータ）を組み込んで測定した結果、熱漏洩
量が約６〜１０％低減し、消費電力量も約２〜３Ｋｗｈ
／月の省エネ化が達成された。Further, as a result of incorporating a refrigeration cycle component (compressor / condenser / evaporator) into a refrigerator having a heat-insulating box formed by foam-filling a rigid polyurethane foam into which a hermetically sealed heat insulating panel is inserted, the heat was measured. The leakage amount is reduced by about 6-10%, and the power consumption is also about 2-3Kwh
/ Month energy saving.
【０１０６】〔比較例 １〕表１に示すポリオールＡ〜
Ｅとヘプタフルオロヨウドエタン（ＨＦＰ）発泡剤を６
０部、水１.０部および反応触媒、整泡剤、イソシアネ
ートを用いて、アルミパネルに発泡充填を行い、サイズ
４８０ｍｍ×３５０ｍｍ×２５ｍｍｔの開放系フォーム
を作製し、熱伝導率を評価した。Comparative Example 1 Polyols A to C shown in Table 1
E and heptafluoroiodoethane (HFP) blowing agent
Using 0 part, 1.0 part of water, a reaction catalyst, a foam stabilizer, and an isocyanate, an aluminum panel was foam-filled to prepare an open foam having a size of 480 mm × 350 mm × 25 mmt, and the thermal conductivity was evaluated.
【０１０７】表１から分かるように、１４.５ｍＷ／ｍ
Ｋと熱伝導率が高く、１ヶ月後の熱伝導率も１５.６ｍ
Ｗ／ｍＫと経時変化が大きい。その後、開放系の断熱パ
ネルを装着してポリオールＦ〜Ｊとシクロペンタンを１
３部と水１.２部を混入し硬質ポリウレタンフォーム材
料の発泡充填を行い、冷凍冷蔵庫の箱体を作製し、コア
層密度と圧縮強度を評価した。As can be seen from Table 1, 14.5 mW / m
High thermal conductivity with K, 15.6m after 1 month
W / mK and changes with time are large. Then, an open insulation panel was attached, and polyols F to J and cyclopentane were added.
3 parts and 1.2 parts of water were mixed and foamed and filled with a rigid polyurethane foam material to prepare a refrigerator-freezer box. The core layer density and the compressive strength were evaluated.
【０１０８】表１から、コア層密度が３７.８ｋｇ／ｍ3
と高く、圧縮強度も０.１０ＭＰａ程であることが分か
った。From Table 1, it can be seen that the core layer density was 37.8 kg / m 3.
It was found that the compressive strength was about 0.10 MPa.
【０１０９】さらに、キャビネット壁内空間の内容積が
約１８０リットルの冷凍冷蔵庫を用い、パック率１１０
％時のウレタン実充填量を調べた結果、６.３５ｋｇの
材料が必要となる。Further, a refrigerator having a cabinet wall having an inner volume of about 180 liters was used.
As a result of examining the actual filling amount of urethane in%, 6.35 kg of material is required.
【０１１０】また、開放系の断熱パネルを挿入した硬質
ポリウレタンフォームを発泡充填し断熱箱体を形成した
冷凍冷蔵庫に、冷凍サイクル部品（圧縮機／コンデンサ
／エバポレータ）を組み込んで測定した結果、熱漏洩量
および消費電力量の低減がほとんど見られなかった。Further, as a result of installing a refrigeration cycle component (compressor / condenser / evaporator) in a refrigerator having a heat-insulating box formed by foam-filling a rigid polyurethane foam into which an open heat-insulating panel is inserted, heat leakage was found. Almost no reduction in power and power consumption was observed.
【０１１１】また、ＨＦＰ発泡剤が、開放系のフォーム
として存在するため、内箱材の汎用ＡＢＳ樹脂へのケミ
カルアタックを引き起こし、発泡剤の回収使用も困難と
なることが分かった。It was also found that since the HFP foaming agent was present as an open foam, it caused a chemical attack on the general-purpose ABS resin of the inner box material, making it difficult to recover and use the foaming agent.
【０１１２】〔比較例 ２〕表１に示すポリオールＡ〜
Ｅとテトラフルオロヨウドエタン（ＴＦＥ）発泡剤を５
０部、水１.５部および反応触媒、整泡剤、イソシアネ
ートを用いて、アルミパネルに発泡充填を行い、サイズ
４８０ｍｍ×３５０ｍｍ×２５ｍｍｔの開放系フォーム
を作製し、熱伝導率を評価した。Comparative Example 2 Polyols A to A shown in Table 1
E and tetrafluoroiodoethane (TFE) blowing agent
Using 0 part, 1.5 parts of water, a reaction catalyst, a foam stabilizer, and an isocyanate, an aluminum panel was foam-filled to prepare an open foam having a size of 480 mm × 350 mm × 25 mmt, and the thermal conductivity was evaluated.
【０１１３】表１から初期の熱伝導率が１４.８ｍＷ／
ｍＫと高く、１ヶ月経過後の熱伝導率も１５.９ｍＷ／
ｍＫと経時変化が大きいことが分かる。From Table 1, the initial thermal conductivity was 14.8 mW /
mK, the thermal conductivity after 1 month is 15.9 mW /
It can be seen that the change over time with mK is large.
【０１１４】その後、開放系の断熱パネルを装着して、
ポリオールＦ〜Ｊとシクロペンタン発泡剤を１６部と水
１.５部を混入した硬質ポリウレタンフォーム材料の発
泡充填を行い、冷凍冷蔵庫の箱体を作製し、コア層密度
と圧縮強度を評価した。表１から、コア層密度が３５.
７ｋｇ／ｍ3と高く、断熱箱体の最終充填部付近にボイ
ド不良が発生した。また、圧縮強度も低く０.０９ＭＰ
ａ程である。After that, an open heat insulating panel was attached,
A rigid polyurethane foam material containing 16 parts of polyols F to J and cyclopentane blowing agent mixed with 1.5 parts of water was foam-filled to prepare a box of a refrigerator, and the core layer density and compressive strength were evaluated. From Table 1, the core layer density was 35.
As high as 7 kg / m 3 , a void defect occurred near the final filling portion of the heat insulating box. In addition, the compression strength is low and 0.09MP
It is about a.
【０１１５】さらに、キャビネット空間の内容積が約１
８０リットルの冷凍冷蔵庫を用いて、パック率１１０％
時のウレタン実充填量を調べた結果、６.１５ｋｇの材
料が必要なことが分かった。Furthermore, when the internal volume of the cabinet space is about 1
Using an 80-liter freezer refrigerator, pack rate 110%
As a result of examining the actual filling amount of urethane at the time, it was found that 6.15 kg of the material was required.
【０１１６】また、開放系の断熱パネルを挿入した硬質
ポリウレタンフォームを発泡充填し断熱箱体を形成した
冷凍冷蔵庫に、冷凍サイクル部品（圧縮機／コンデンサ
／エバポレータ）を組み込んで測定した結果、熱漏洩量
および消費電力量の低減がほとんど見られなかった。ま
た、ＴＦＥ発泡剤が開放系のフォームに存在するため、
内箱材の汎用ＡＢＳ樹脂へケミカルアタックを引き起こ
し、回収使用が困難になる。Further, as a result of incorporating a refrigeration cycle component (compressor / condenser / evaporator) into a refrigerator having a heat-insulating box formed by foam-filling a rigid polyurethane foam into which an open heat-insulating panel is inserted, heat leakage was measured. Almost no reduction in power and power consumption was observed. Also, because the TFE blowing agent is present in the open foam,
It causes chemical attack on the general-purpose ABS resin of the inner box material, and makes recovery and use difficult.
【０１１７】〔比較例 ３〕表１に示すポリオールＡ〜
ＥとＰＦＥ発泡剤を４０部、シクロペンタン（ＣＰ）発
泡剤を１０部と水１.０部および反応触媒、整泡剤、イ
ソシアネートを用いてアルミパネルに発泡充填を行い、
サイズ４８０ｍｍ×３５０ｍｍ×２５ｍｍｔの開放系フ
ォームを作製し、熱伝導率を評価した。[Comparative Example 3] Polyols A to
40 parts of E and PFE foaming agent, 10 parts of cyclopentane (CP) foaming agent, 1.0 part of water, foam filling of aluminum panel using reaction catalyst, foam stabilizer, isocyanate,
An open foam having a size of 480 mm × 350 mm × 25 mmt was prepared, and the thermal conductivity was evaluated.
【０１１８】表１から初期の熱伝導率が１５.３ｍＷ／
ｍＫと高く、１ヶ月経過後の熱伝導率も１６.３ｍＷ／
ｍＫと経時変化が大きくことが分かる。From Table 1, the initial thermal conductivity was 15.3 mW /
mK, and the thermal conductivity after 1 month is 16.3 mW /
It turns out that mK and a change with time are large.
【０１１９】その後、開放系の断熱パネルを装着してポ
リオールＦ〜Ｊとシクロペンタン発泡剤を１８部と水
１.６部を混入した硬質ポリウレタンフォーム材料の発
泡充填を行い、コア層密度と圧縮強度を評価した。表１
から、コア層密度が３６.８ｋｇ／ｍ3と高く最終充填部
付近にボイド不良が発生した。また、圧縮強度も低く
０.８ＭＰａ程である。After that, an open insulation panel was attached, and a rigid polyurethane foam material containing 18 parts of polyols F to J, cyclopentane foaming agent and 1.6 parts of water was mixed and foamed and filled. The strength was evaluated. Table 1
As a result, the core layer density was as high as 36.8 kg / m 3, and void defects occurred near the final filling portion. Also, the compressive strength is low, about 0.8 MPa.
【０１２０】さらに、キャビネット空間の内容積が約１
８０リットルの冷凍冷蔵庫を用いて、パック率１１０％
時のウレタン実充填量を調べた結果、６.２５ｋｇの材
料が必要なことが分かった。Further, the inner volume of the cabinet space is about 1
Using an 80-liter freezer refrigerator, pack rate 110%
As a result of examining the actual filling amount of urethane at the time, it was found that 6.25 kg of the material was required.
【０１２１】また、開放系の断熱パネルを挿入した硬質
ポリウレタンフォームを発泡充填し断熱箱体を形成した
冷凍冷蔵庫に、冷凍サイクル部品（圧縮機／コンデンサ
／エバポレータ）を組み込んで測定した結果、熱漏洩量
および消費電力量の低減がほとんど見られなかった。ま
た、ＰＦＥとＣＰ発泡剤が開放系のフォームに存在する
ため、内箱材の汎用ＡＢＳ樹脂へケミカルアタックを引
き起こし、また、混合系発泡剤であるため回収も困難で
ある。Further, as a result of incorporating a refrigeration cycle component (compressor / condenser / evaporator) into a refrigerator having a heat-insulated box formed by foam-filling a rigid polyurethane foam into which an open heat-insulating panel is inserted, heat leakage was found. Almost no reduction in power and power consumption was observed. Further, since the PFE and the CP foaming agent are present in the open foam, they cause a chemical attack on the general-purpose ABS resin of the inner box material, and it is difficult to collect them because of the mixed foaming agent.
【０１２２】〔比較例 ４〕実施例１に示す密閉封着型
の断熱パネルを装着して、ポリオールＦ〜Ｊとシクロペ
ンタン発泡剤を２０部と水２.０部を混入した硬質ポリ
ウレタンフォーム材料の発泡充填を行い、冷凍冷蔵庫の
箱体を作製し、コア層密度と圧縮強度を評価した。[Comparative Example 4] A rigid polyurethane foam material to which the hermetically sealed heat insulating panel shown in Example 1 was attached, and polyols F to J, 20 parts of cyclopentane blowing agent and 2.0 parts of water were mixed. Was foam-filled to prepare a refrigerator-freezer box, and the core layer density and the compressive strength were evaluated.
【０１２３】表１から、コア層密度が３０.５ｋｇ／ｍ3
と低くなる。しかし、圧縮強度が０.０６Ｍｐａまで低
減しフォーム収縮の発生により、断熱箱体不良の歪が発
生してしまった。As shown in Table 1, the core layer density was 30.5 kg / m 3.
And lower. However, the compressive strength was reduced to 0.06 MPa, and the shrinkage of the foam caused the deformation of the heat-insulating box.
【０１２４】〔比較例 ５〕実施例２に示す密閉封着型
の断熱パネルを装着して、ポリオールＦ〜Ｊとシクロペ
ンタン発泡剤を１６部と水１.３部を混入し硬質ポリウ
レタンフォーム材料の発泡充填を行い、冷凍冷蔵庫の箱
体を作製して、コア層密度と圧縮強度を評価した。[Comparative Example 5] A rigid polyurethane foam material was prepared by mounting the hermetically sealed heat insulating panel shown in Example 2 and mixing polyols F to J, 16 parts of cyclopentane blowing agent and 1.3 parts of water. Was foam-filled to prepare a refrigerator-freezer box, and the core layer density and the compressive strength were evaluated.
【０１２５】表１から、コア層密度が３５.０ｋｇ／ｍ3
と高く、最終充填部付近にボイド不良が発生した。ま
た、圧縮強度も低く０.０９Ｍｐａ程である。さらに、
キャビネット壁内空間の内容積について約１８０リット
ルの冷凍冷蔵庫を用い、パック率が１１０％時のウレタ
ン実充填量を調べた結果、６.０５ｋｇの材料が必要で
ありウレタン充填量の低減は困難であった。As shown in Table 1, the core layer density was 35.0 kg / m 3.
And a void defect occurred near the final filling portion. Also, the compressive strength is low, about 0.09 Mpa. further,
As a result of examining the actual filling amount of urethane when the packing ratio is 110% using a refrigerator of about 180 liters for the inner volume of the space in the cabinet wall, 6.05 kg of material is required, and it is difficult to reduce the filling amount of urethane. there were.
【０１２６】本実施例の断熱部材は、熱伝導率が非常に
低い密閉封着型断熱パネルと、シクロペンタン発泡剤を
用いた低密度・高流動性の硬質ポリウレタンフォームを
組合せたことにより、シクロペンタン発泡剤でも熱漏洩
量低減による省エネ化および低密度ウレタン使用による
充填量の低減が達成された。The heat insulating member of this example is a combination of a hermetically sealed heat insulating panel having a very low thermal conductivity and a low-density and high-flow hard polyurethane foam using a cyclopentane blowing agent. The pentane foaming agent also achieved energy savings by reducing the amount of heat leakage and reduced filling by using low-density urethane.
【０１２７】なお、前記実施例では、いずれも断熱フォ
ームとして独立気泡のものを用いて行ったが、連通気泡
の断熱フォームを併用することも可能である。In each of the above embodiments, a closed-cell foam was used as the heat-insulating foam. However, it is also possible to use a heat-insulating foam having open cells.
【０１２８】[0128]
【発明の効果】本発明によれば、外箱と内箱で構成され
た断熱箱体の断熱壁の断熱部材に、独立構造の気泡を有
し、熱伝導率が１３.５ｍＷ／ｍＫ以下の密閉封着型断
熱パネルと、シクロペンタン発泡剤を用いた低密度の硬
質ポリウレタンフォームを組合わせて用いることによ
り、地球環境に優しいシクロペンタン発泡剤でも、熱漏
洩量低減を図ることが可能となり、省エネ化並びに低密
度のウレタン使用による充填量の低減が可能となり、低
コスト化や歩留まり向上を図ることが可能な保冷装置を
提供することができる。According to the present invention, the heat insulating member of the heat insulating wall of the heat insulating box composed of the outer box and the inner box has an air bubble of an independent structure and a heat conductivity of 13.5 mW / mK or less. By using a combination of a hermetically sealed insulation panel and a low-density rigid polyurethane foam using a cyclopentane foaming agent, it is possible to reduce the amount of heat leakage even with a cyclopentane foaming agent that is environmentally friendly, Energy saving and reduction of the filling amount by using low-density urethane can be achieved, and a cold storage device capable of reducing cost and improving yield can be provided.
【図１】冷凍冷蔵庫の全体模式斜視図である。FIG. 1 is an overall schematic perspective view of a refrigerator-freezer.
【図２】密閉封着型断熱パネルを挿入した断熱箱体の模
式斜視図である。FIG. 2 is a schematic perspective view of a heat insulating box in which a hermetically sealed heat insulating panel is inserted.
【図３】密閉封着型断熱パネル挿入細部の断熱箱体の平
面模式断面図である。FIG. 3 is a schematic cross-sectional plan view of a heat-insulating box body with details of insertion of a hermetically sealed heat-insulating panel.
【図４】４点注入により硬質ウレタンフォームを充填す
る模式斜視図である。FIG. 4 is a schematic perspective view of filling a rigid urethane foam by four-point injection.
１…断熱箱体、２…外箱、３…内箱、４…密閉封着型断
熱パネル、５…接着剤、６…硬質ウレタンフォーム、７
…ウレタン注入ヘッド、８…ウレタンの流れ、９…ウレ
タン注入口、１０…サンプル採取部、１１…測定サンプ
ル。DESCRIPTION OF SYMBOLS 1 ... Insulated box, 2 ... Outer box, 3 ... Inner box, 4 ... Hermetically sealed heat insulating panel, 5 ... Adhesive, 6 ... Rigid urethane foam, 7
... Urethane injection head, 8: urethane flow, 9: urethane injection port, 10: sample collection section, 11: measurement sample.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 荒木 邦成 栃木県下都賀郡大平町大字富田800番地 株式会社日立製作所冷熱事業部内 (72)発明者 福田 克美 栃木県下都賀郡大平町大字富田800番地 株式会社日立製作所冷熱事業部内 (72)発明者 皆川 昭宏 栃木県下都賀郡大平町大字富田800番地 株式会社日立製作所冷熱事業部内 Ｆターム(参考） 3L102 JA01 JA03 LB01 LB31 MA01 MA07 MB04 MB17 MB21 MB31 4F100 AB01D AK51A AK51C AK74E AR00B AT00D AT00E BA03 BA05 BA07 BA10A BA10D BA10E CA02A CA02C DJ02A DJ02C GB48 GB90 JA13A JA13C JD01B JJ02 JJ02B JL00 YY00A YY00C ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kunari Araki 800, Tomita, Odaimachi, Ohira-cho, Shimotsuga-gun, Tochigi Prefecture Inside the Hitachi, Ltd.Cooling Division (72) Katsumi Fukuda 800, Tomita, Oda-machi, Ohira-cho, Shimotsuga-gun, Tochigi Co., Ltd. Hitachi, Ltd.Cooling Division (72) Inventor Akihiro Minagawa 800, Tomita, Ohira-cho, Shimotsuga-gun, Tochigi Prefecture F-term (Ref.) AR00B AT00D AT00E BA03 BA05 BA07 BA10A BA10D BA10E CA02A CA02C DJ02A DJ02C GB48 GB90 JA13A JA13C JD01B JJ02 JJ02B JL00 YY00A YY00C
Claims (5)
の断熱壁を構成する断熱材が、ぺンタフルオロヨウドエ
タンと水の混合発泡剤を用いた独立構造の気泡を有する
硬質ポリウレタンフォームと、ガスバリア性の密閉封着
型断熱パネルと、シクロペンタンと水の混合発泡剤で発
泡された硬質ポリウレタンフォームにより構成されてい
ることを特徴とする保冷装置。1. A heat insulating material constituting a heat insulating wall between an outer box and an inner box of a heat insulating box body of a cold storage device has air bubbles of an independent structure using a mixed foaming agent of pentafluoroiodoethane and water. A cold insulation device comprising a rigid polyurethane foam, a gas barrier hermetically sealed heat insulating panel, and a rigid polyurethane foam foamed with a mixed foaming agent of cyclopentane and water.
が、外箱鉄板内面側にガスバリア性の密閉封着型断熱パ
ネルで遮蔽され、シクロペンタンおよび水の混合発泡剤
で発泡された硬質ポリウレタンフォームが充填されてい
る請求項１に記載の保冷装置。2. A heat insulating material constituting a heat insulating wall of the heat insulating box is shielded on the inner surface side of the outer box iron plate by a gas barrier airtight sealing type heat insulating panel, and foamed with a mixed foaming agent of cyclopentane and water. The cooling device according to claim 1, wherein the device is filled with a rigid polyurethane foam.
ア性の袋中にゲッタ剤および／またはアルカリ金属の水
酸化物を一緒に挿入した断熱パネルである請求項１また
は２に記載の保冷装置。3. The cooling device according to claim 1, wherein the hermetically sealed heat insulating panel is a heat insulating panel in which a getter agent and / or an alkali metal hydroxide are inserted together into a gas barrier bag. .
発泡された硬質ポリウレタンフォームが、コア層密度３
１〜３４ｋｇ／ｍ3である請求項１，２または３に記載
の保冷装置。4. The rigid polyurethane foam foamed with the mixed foaming agent of cyclopentane and water has a core layer density of 3.
Cooler according to claim 1, 2 or 3 is 1~34kg / m 3.
ル，ブタジエンゴム，スチレン共重合体からなる汎用Ａ
ＢＳ樹脂で構成されている請求項１〜４のいずれかに記
載の保冷装置。5. The general-purpose A made of acrylonitrile, butadiene rubber, and styrene copolymer, wherein the inner box of the heat insulating box is made of
The cool storage device according to any one of claims 1 to 4, which is made of a BS resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10348220A JP2000171148A (en) | 1998-12-08 | 1998-12-08 | Cooling device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10348220A JP2000171148A (en) | 1998-12-08 | 1998-12-08 | Cooling device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000171148A true JP2000171148A (en) | 2000-06-23 |
Family
ID=18395561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10348220A Pending JP2000171148A (en) | 1998-12-08 | 1998-12-08 | Cooling device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000171148A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006153150A (en) * | 2004-11-30 | 2006-06-15 | Kurabo Ind Ltd | Vacuum insulation |
| CN104048472A (en) * | 2013-03-15 | 2014-09-17 | 佛山海尔电冰柜有限公司 | Heat insulation component and forming method of heat insulation component |
| EP2894423B1 (en) * | 2012-09-10 | 2017-11-29 | Panasonic Intellectual Property Management Co., Ltd. | Refrigerator |
| US10480714B2 (en) | 2013-03-29 | 2019-11-19 | Ihi Corporation | Low temperature liquid tank |
| CN114390976A (en) * | 2019-09-19 | 2022-04-22 | 巴斯夫欧洲公司 | Enhancement of long-term properties of closed-cell rigid polyurethane foams |
-
1998
- 1998-12-08 JP JP10348220A patent/JP2000171148A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006153150A (en) * | 2004-11-30 | 2006-06-15 | Kurabo Ind Ltd | Vacuum insulation |
| EP2894423B1 (en) * | 2012-09-10 | 2017-11-29 | Panasonic Intellectual Property Management Co., Ltd. | Refrigerator |
| CN104048472A (en) * | 2013-03-15 | 2014-09-17 | 佛山海尔电冰柜有限公司 | Heat insulation component and forming method of heat insulation component |
| US10480714B2 (en) | 2013-03-29 | 2019-11-19 | Ihi Corporation | Low temperature liquid tank |
| CN114390976A (en) * | 2019-09-19 | 2022-04-22 | 巴斯夫欧洲公司 | Enhancement of long-term properties of closed-cell rigid polyurethane foams |
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