WO2021157698A1 - フェノール樹脂発泡体積層板 - Google Patents
フェノール樹脂発泡体積層板 Download PDFInfo
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- WO2021157698A1 WO2021157698A1 PCT/JP2021/004337 JP2021004337W WO2021157698A1 WO 2021157698 A1 WO2021157698 A1 WO 2021157698A1 JP 2021004337 W JP2021004337 W JP 2021004337W WO 2021157698 A1 WO2021157698 A1 WO 2021157698A1
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- WIPO (PCT)
- Prior art keywords
- phenol resin
- resin foam
- mass
- less
- surface material
- Prior art date
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 233
- 239000006260 foam Substances 0.000 title claims abstract description 147
- 239000000463 material Substances 0.000 claims abstract description 105
- 229920001568 phenolic resin Polymers 0.000 claims description 26
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 20
- 239000000123 paper Substances 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000004745 nonwoven fabric Substances 0.000 claims description 10
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 7
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- 239000002759 woven fabric Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 85
- 239000004088 foaming agent Substances 0.000 description 39
- 238000000034 method Methods 0.000 description 33
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000005187 foaming Methods 0.000 description 21
- -1 fire doors Substances 0.000 description 19
- 239000002667 nucleating agent Substances 0.000 description 19
- 230000002378 acidificating effect Effects 0.000 description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 12
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 239000008259 solid foam Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 5
- 238000011417 postcuring Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 3
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 150000003739 xylenols Chemical class 0.000 description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 2
- USVVENVKYJZFMW-ONEGZZNKSA-N (e)-carboxyiminocarbamic acid Chemical compound OC(=O)\N=N\C(O)=O USVVENVKYJZFMW-ONEGZZNKSA-N 0.000 description 2
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000000752 ionisation method Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
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- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-N 0.000 description 1
- NLOLSXYRJFEOTA-OWOJBTEDSA-N (e)-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)\C=C\C(F)(F)F NLOLSXYRJFEOTA-OWOJBTEDSA-N 0.000 description 1
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- GDPWRLVSJWKGPJ-OWOJBTEDSA-N (e)-1-chloro-2,3,3,3-tetrafluoroprop-1-ene Chemical compound Cl/C=C(/F)C(F)(F)F GDPWRLVSJWKGPJ-OWOJBTEDSA-N 0.000 description 1
- ZHJBJVPTRJNNIK-UPHRSURJSA-N (z)-1,2-dichloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(\Cl)=C\Cl ZHJBJVPTRJNNIK-UPHRSURJSA-N 0.000 description 1
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- CVMVAHSMKGITAV-UHFFFAOYSA-N 1,1,1,4,4,5,5,5-octafluoropent-2-ene Chemical compound FC(F)(F)C=CC(F)(F)C(F)(F)F CVMVAHSMKGITAV-UHFFFAOYSA-N 0.000 description 1
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- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
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- CDOOAUSHHFGWSA-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropene Chemical compound FC=CC(F)(F)F CDOOAUSHHFGWSA-UHFFFAOYSA-N 0.000 description 1
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- SEXCLMKCCLUUKC-UHFFFAOYSA-N 1-chloro-1,3,3-trifluoroprop-1-ene Chemical compound FC(F)C=C(F)Cl SEXCLMKCCLUUKC-UHFFFAOYSA-N 0.000 description 1
- USCSECLOSDIOTA-UHFFFAOYSA-N 1-chloro-2,3,3-trifluoroprop-1-ene Chemical compound FC(F)C(F)=CCl USCSECLOSDIOTA-UHFFFAOYSA-N 0.000 description 1
- CZHLPWNZCJEPJB-UHFFFAOYSA-N 1-chloro-3-methylbutane Chemical compound CC(C)CCCl CZHLPWNZCJEPJB-UHFFFAOYSA-N 0.000 description 1
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- IAOGXBHBKZGVGJ-UHFFFAOYSA-N 2,3,3-trichloro-3-fluoroprop-1-ene Chemical compound FC(Cl)(Cl)C(Cl)=C IAOGXBHBKZGVGJ-UHFFFAOYSA-N 0.000 description 1
- IAPGBTZUBKUKOR-UHFFFAOYSA-N 2,3-dichloro-3,3-difluoroprop-1-ene Chemical compound FC(F)(Cl)C(Cl)=C IAPGBTZUBKUKOR-UHFFFAOYSA-N 0.000 description 1
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- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/20—Ternary blends of expanding agents
- C08J2203/202—Ternary blends of expanding agents of physical blowing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
- C08J2361/10—Phenol-formaldehyde condensates
Definitions
- the present invention relates to a phenol resin foam laminated board, and more particularly to a phenol resin foam laminated board having less oozing stains from the surface material.
- Acid-curable phenol resin foam made from resole-type phenol resin is hard to burn, emits less smoke, and has good heat insulation properties. Therefore, for example, outer wall materials such as metal siding, partition panels, etc. In addition to interior wall materials, it is used for ceiling materials, fire doors, and building materials such as rain doors.
- the acid-curable phenol resin foam is also widely used as a cold and heat insulating material for building materials and industrial plants.
- Patent Document 1 discloses that a combination of HCFO-1224yd (Z) and other foaming agents can be used for the phenol resin foam.
- Patent Document 2 discloses that the thermal conductivity can be reduced by using HCFO-1224yd (Z) in a urethane resin foam which is the same thermosetting resin foam.
- Patent Documents 1 and 2 simultaneously suppress the emission from the foamable resin composition due to the characteristics of HCFO-1224yd (Z) and the decrease in viscosity due to plasticization.
- the heat insulating performance was lowered, and the exudation of the foamable resin composition to the surface material could not be suppressed.
- HCFO-1224yd (Z) has the lowest thermal conductivity among HCFOs, the component ratio of HCFO-1224yd (Z) in the foaming agent, particularly the mole of HCFO-1224yd (Z) filled in the phenol resin foam. The amount affects the insulation performance.
- HCFO-1224yd (Z) has a low boiling point in HCFO, the foamable phenol resin composition discharged onto the surface material is easily dissipated before curing and is filled in the phenol resin foam.
- HCFO-1224yd Z
- HCFO-1224yd Z
- a method for reducing the exudation of the foamable phenol resin composition from the surface material has been found, and the above-mentioned problems have been solved.
- the present invention provides the following [1] to [5].
- a phenol resin foam laminated plate in which a flexible surface material is arranged on at least one of one surface of the phenol resin foam and the back surface of the one surface, and the phenol resin foam is HCFO-1224yd (Z). ),
- the density is 20 kg / m 3 or more and 55 kg / m 3 or less
- the closed cell ratio is 80% or more
- the average cell diameter is 60 ⁇ m or more and 200 ⁇ m or less
- the exudation area ratio from the surface material is 30% or less.
- said phenolic resin foamed body space volume 22.4 ⁇ 10 -3 m 3 per content of HCFO-1224yd (Z) is less than 0.35mol least 0.06 mol, phenolic foam laminate ..
- the phenolic resin foam laminate according to [1] which contains at least one gas component selected from an aliphatic hydrocarbon having 6 or less carbon atoms and a chlorinated saturated hydrocarbon having 5 or less carbon atoms.
- the present invention it is possible to provide a high-performance phenol resin foam laminated board having high heat insulating performance, less exudation of the foamable phenol resin composition from the surface material, and having a good appearance.
- the phenol resin foam laminated board (hereinafter, may be referred to as “foam laminated board”) in the present embodiment exists in a state in which a large number of bubbles are dispersed in the cured phenol resin formed by the curing reaction. It is a laminate provided with a phenol resin foam and a surface material on at least one side of the phenol resin foam and the back surface of the one side.
- the foam laminated board of the present embodiment has less exudation of the foamable phenol resin composition from the surface material, and the upper and lower surface materials can be peeled off. Therefore, the surface material is peeled off.
- the "thickness direction" in the present embodiment refers to the dimension of the shortest side of the three sides of the foam laminated board, and usually, the foamable phenol resin composition on the lower surface material at the time of manufacturing the foam laminated board. Is in the direction of foaming and growing.
- the phenolic resin foam laminate is used alone or in various applications by joining it with an external member.
- the external member include one and a combination of a board-shaped material and a sheet-shaped / film-shaped material.
- Board-like materials include ordinary plywood, structural plywood, particle board, and wood-based boards such as OSB, wood wool cement board, wood piece cement board, gypsum board, flexible board, medium density fiber board, calcium silicate board, and Kay.
- a magnesium acid plate and a volcanic vitreous multi-layer plate are suitable.
- polyester non-woven fabric polypropylene non-woven fabric, inorganic-filled glass fiber non-woven fabric, glass fiber non-woven fabric, paper, calcium carbonate paper, polyethylene processed paper, polyethylene film, plastic moisture-proof film, asphalt waterproof paper, and Aluminum foil (with or without holes) is suitable.
- the density of the phenol resin foam of the phenol resin foam laminate of the present embodiment is 20 kg / m 3 or more and 55 kg / m 3 or less, preferably 22 kg / m 3 or more and 50 kg / m 3 or less, more preferably. It is 24 kg / m 3 or more and 45 kg / m 3 or less, more preferably 26 kg / m 3 or more and 40 kg / m 3 or less, and most preferably 26 kg / m 3 or more and 36 kg / m 3 or less.
- the density is 20 kg / m 3 or more, mechanical strength such as compressive strength and bending strength can be ensured, and it is possible to avoid damage during handling of the foam.
- the density of the phenol resin foam may be adjusted by adjusting the filling ratio of the foaming agent into the phenol resin foam, mainly the ratio of the foaming agent charged into the phenol resin foam, the temperature of the foamable phenol resin composition, and the like.
- the closed cell ratio of the phenol resin foam of the phenol resin foam laminate is 80% or more, preferably 85% or more, more preferably 88% or more, further preferably 90% or more, and most preferably 92% or more. be.
- the closed cell ratio of the phenol resin foam is adjusted to a desired value by changing, for example, the amount of the foam nucleating agent added, the amount of the foaming agent added, and the amount of the organic acid used as the acidic curing agent. can.
- the average cell diameter of the phenol resin foam of the phenol resin foam laminate is 60 ⁇ m or more and 200 ⁇ m or less, preferably 65 ⁇ m or more and 180 ⁇ m or less, more preferably 70 ⁇ m or more and 155 ⁇ m or less, and most preferably 75 ⁇ m or more and 130 ⁇ m or less. Is.
- the average cell diameter is 60 ⁇ m or more, it is possible to suppress an increase in the density of the foam. As a result, the heat transfer ratio of the resin portion in the foam can be reduced, so that the heat insulating performance of the phenol resin foam can be ensured.
- the average cell diameter of the phenol resin foam is determined, for example, by the amount of the solid foam nucleating agent added, the temperature of the foamable phenol resin composition, and the step of discharging the mixed foamable phenol resin composition onto the lower surface material. It can be adjusted to a desired value by changing the timing of molding, the ratio of the amount of the foaming agent added to the amount of the organic acid used as the acidic curing agent, and the curing conditions such as temperature and residence time.
- the thermal conductivity of the phenolic resin foam laminate measured in an environment of 23 ° C. is preferably 0.185 W / m ⁇ K or less, more preferably 0.0182 W / m ⁇ K or less, and even more preferably 0. It is 0178 W / m ⁇ K or less, particularly preferably 0.0174 W / m ⁇ K or less, and most preferably 0.0170 W / m ⁇ K or less.
- the phenol resin foam of the phenol resin foam laminate contains HCFO-1224yd (Z), for example, a phenol resin, a surfactant, a foaming agent containing HCFO-1224yd (Z), and a solid. It is produced from a foaming phenol resin composition containing a foaming nucleating agent and an acidic curing agent containing an organic acid.
- the effervescent phenol resin composition may optionally contain a component other than the above, for example, a phthalate compound or the like.
- a resol type phenol resin synthesized from an alkali metal hydroxide or an alkaline earth metal hydroxide is used as the phenol resin.
- the resol type phenol resin is synthesized by heating phenols and aldehydes as raw materials with an alkaline catalyst in a temperature range of 40 to 100 ° C.
- an additive such as urea may be added during or after the synthesis of the resol type phenol resin.
- the resol-type phenol resin after synthesis usually contains an excess amount of water, the amount of water is adjusted to be suitable for foaming at the time of foaming.
- the phenol resin contains an aliphatic hydrocarbon or an alicyclic hydrocarbon having a high boiling point, a mixture thereof, a diluent for adjusting the viscosity such as ethylene glycol and diethylene glycol, and other additives as necessary. It can also be added.
- the starting molar ratio of phenols to aldehydes during the synthesis of the phenolic resin is preferably in the range of 1: 1 to 1: 4.5, more preferably in the range of 1: 1.5 to 1: 2.5. Is.
- the phenols preferably used in the synthesis of the phenol resin in the present embodiment are phenol itself and other phenols, and examples of other phenols include resorcinol, catechol, o-, and m-. And p-cresol, xylenols, ethylphenols, p-tert butylphenol and the like. Also, dinuclear phenols can be used.
- the aldehydes may be any compound that can serve as an aldehyde source, and as the aldehydes, formaldehyde itself, paraformaldehyde that can be depolymerized and used, and other aldehydes and derivatives thereof are preferably used.
- aldehydes include glyoxal, acetaldehyde, chloral, furfural, benzaldehyde and the like.
- Urea, dicyandiamide, melamine and the like may be added to the phenol resin as additives. In the present specification, when these additives are added, the "phenolic resin" refers to those after the additives have been added.
- phenol resin to which a surfactant is added is referred to as a "phenol resin composition”
- a foaming agent, a solid foam nucleating agent and an acid curing are applied to the "phenol resin composition”.
- a composition obtained by adding an agent to impart foamability and curability is referred to as a “foamable phenol resin composition”.
- the resin portion after forming the phenol resin foam is referred to as a "phenol resin cured product”.
- the mass average molecular weight of the phenol resin is preferably 900 or more, more preferably 1,000 or more, further preferably 1,150 or more, and most preferably 1,300 or more.
- the mass average molecular weight is preferably 2,500 or less, more preferably 2,200 or less, further preferably 2,050 or less, and most preferably 1,900 or less.
- the mass average molecular weight of the phenol resin when the mass average molecular weight of the phenol resin is 2,500 or less, it becomes easy to suppress the seepage of the effervescent phenol resin composition.
- the mass average molecular weight of the phenol resin can be measured by using the method described in the examples of the present specification.
- the viscosity of the phenol resin and the phenol resin composition at 40 ° C. is preferably 5,000 mPa ⁇ s or more and 100,000 mPa ⁇ s or less, more preferably 7,000 mPa ⁇ s or more and 50,000 mPa ⁇ s or less, and further. It is preferably 9,000 mPa ⁇ s or more and 40,000 mPa ⁇ s or less.
- the water content of the phenol resin and the phenol resin composition is preferably 1.5% by mass or more and 30% by mass or less.
- the surfactant, foaming agent and solid foam nucleating agent contained in the effervescent phenol resin composition may be added in advance to the phenol resin or may be added at the same time as the acidic curing agent.
- alkylene which is a copolymer of ethylene oxide and propylene oxide.
- Oxide a condensate of alkylene oxide and castor oil, a condensation product of alkylene oxide with alkylphenol such as nonylphenol and dodecylphenol, and polyoxyethylene alkyl ether having 14 to 22 carbon atoms in the alkyl ether moiety.
- fatty acid esters such as polyoxyethylene fatty acid esters, silicone compounds such as polydimethylsiloxane, polyalcohols and the like are preferable.
- These surfactants may be used alone or in combination of two or more.
- the amount used is not particularly limited, but is preferably used in the range of 0.3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the phenol resin.
- the foaming agent contains HCFO-1224yd (Z) as a constituent component. Further, the foaming agent contains at least one selected from an aliphatic hydrocarbon having 6 or less carbon atoms and a chlorinated saturated hydrocarbon having 5 or less carbon atoms as a constituent component of the foaming agent other than HCFO-1224yd (Z). It is preferable to be.
- aliphatic hydrocarbon having 6 or less carbon atoms a known foaming agent can be used.
- isobutane, normal butane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane and the like can be mentioned.
- These hydrocarbons may be used alone or in combination of two or more.
- chlorinated saturated hydrocarbon having 5 or less carbon atoms a linear or branched hydrocarbon having 2 to 5 carbon atoms can be used.
- the number of bonded chlorine atoms is not limited, but is preferably 1 to 4, and examples of the chlorinated aliphatic hydrocarbon include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, and pentyl. Chloride, isopentyl chloride and the like can be mentioned. Of these, propyl chloride and isopropyl chloride, which are chloropropanes, are more preferably used.
- the foaming agent may contain a hydrofluoroolefin (at least one of a chlorinated hydrofluoroolefin and a non-chlorinated hydrofluoroolefin) other than HCFO-1224yd (Z).
- a hydrofluoroolefin at least one of a chlorinated hydrofluoroolefin and a non-chlorinated hydrofluoroolefin
- chlorinated hydrofluoroolefin other than HCFO-1224yd (Z) examples include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd, for example, E form (HCFO-1233zd (E)), Honeywell.
- non-chlorinated hydrofluoroolefin examples include 1,3,3,3-tetrafluoropropa-1-ene (HFO-1234ze, for example, E-form (HFO-1234ze (E))) manufactured by Honeywell Japan Co., Ltd.
- Opteon TM 1100 2,3,3,3-tetrafluoro-1-propen (HFO-1234yf), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1 , 3,3,3-tetrafluoropropene (HFO-1234ze), 3,3,3-trifluoropropene (HFO-1243zf), and 1,1,1,4,4,5,5,5-octafluoro -2-pentene (HFO-1438mzz) and the like are mentioned, and one or a mixture of these conformational isomers, that is, E-form or Z-form, is used.
- the other foaming agent is not particularly limited, and for example, sodium hydrogen carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, azodicarboxylic acid amide, azobisisobutyronitrile, barium azodicarboxylic acid, N, N'.
- Examples thereof include chemical foaming agents such as -dinitrosopentamethylenetetramine, p, p'-oxybisbenzenesulfonylhydrazide, and trihydrazinotriazine. These foaming agents may be used alone or in combination of two or more.
- the amount of the foaming agent in the foamable phenol resin composition varies depending on the foaming and curing conditions such as the type of foaming agent, compatibility with the phenol resin, temperature, and residence time, but is the total of the phenol resin and the surfactant. It is preferably 4.0 parts by mass or more and 11.0 parts by mass or less, more preferably 4.5 parts by mass or more and 10.5 parts by mass or less, and 5.0 parts by mass or more with respect to 100 parts by mass. It is more preferably 10.0 parts by mass or less. When the amount of the foaming agent per 100 parts by mass of the total of the phenol resin and the surfactant is 4.0 parts by mass or more, it is possible to suppress the increase in the density of the phenol resin foam.
- the total amount of the phenol resin and the surfactant is 11.0 parts by mass or less per 100 parts by mass, it is suppressed that the phenol resin foam has a low density, and the phenol resin foam has a density having an appropriate strength.
- the bubble wall surface is less likely to crack, and it becomes easier to suppress a decrease in the closed cell ratio.
- the content of HCFO-1224yd (Z) is a phenolic resin foamed body space volume 22.4 ⁇ 10 -3 m 3 per not less than 0.06 mol 0.35 mol or less, preferably 0.11mol It is 0.35 mol or less, more preferably 0.15 mol or more and 0.35 mol or less, further preferably 0.15 mol or more and 0.30 mol or less, and most preferably 0.15 mol or more and 0.25 mol or less.
- the amount of HCFO-1224yd (Z) is 0.06 mol or more, low thermal conductivity of the phenol resin foam and the phenol resin foam laminated board is realized.
- the amount of HCFO-1224yd (Z) is 0.35 mol or less, it is possible to suppress a decrease in the viscosity of the foamable phenol resin composition due to the plasticization of the resin due to its high affinity with the phenol resin, and to suppress the decrease in viscosity from the surface material. It is possible to suppress the seepage of the effervescent phenol resin composition.
- Solid foam nucleating agents include aluminum hydroxide powder, aluminum oxide powder, calcium carbonate powder, talc, clay (kaolin), silica stone powder, silica sand, mica, calcium silicate powder, wallastnite, glass powder, and glass beads.
- Inorganic powders such as fly ash, silica fume, gypsum powder, broom sand, slag powder, alumina cement, Portoland cement, and organic powders such as crushed powder of phenolic resin foam can also be added. These may be used alone or in combination of two or more.
- the solid foaming nucleating agent may be present in the effervescent phenol resin composition, and the timing of its addition is not particularly limited, but it is generally added to the phenol resin composition or in a mixing step described later. It is added at the same time as the foaming agent.
- the amount of the solid foam nucleating agent added is preferably 3.0 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the phenol resin composition, and is 4.0 parts by mass or more and 8.0 parts by mass or less. The following is more preferable.
- the amount of the solid foam nucleating agent added is 3.0 parts by mass or more, it becomes difficult to suppress the exudation of the foamable phenol resin composition from the surface material.
- by setting the addition amount of the solid foaming nucleating agent to 10.0 parts by mass or less, it becomes easy to suppress the emission of HCFO-1224yd (Z), which is a foaming agent having a low boiling point.
- the acidic curing agent may be any acidic curing agent capable of curing the phenol resin composition, and contains an organic acid as an acid component.
- organic acid aryl sulfonic acid or an anhydride thereof is preferable.
- aryl sulfonic acid and its anhydride include toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, substituted phenol sulfonic acid, xylenol sulfonic acid, substituted xylenol sulfonic acid, dodecylbenzene sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid and the like.
- resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol and the like may be added as a curing aid. Further, these curing agents may be diluted with a solvent such as ethylene glycol and diethylene glycol.
- the amount of the acidic curing agent used varies depending on the type, and when a mixture of 60% by mass of paratoluenesulfonic acid monohydrate and 40% by mass of diethylene glycol is used, a total of 100 of the phenol resin and the surfactant is used. It is preferably used in an amount of 8 parts by mass or more and 20 parts by mass or less, and more preferably 10 parts by mass or more and 15 parts by mass or less with respect to parts by mass.
- a flexible surface material (flexible surface material) is used as the surface material arranged on at least one of one surface of the phenol resin foam and the back surface of the one surface.
- the flexible surface materials used include non-woven fabrics or woven fabrics whose main components are polyester, polypropylene, nylon and the like, kraft paper, glass fiber mixed paper, calcium hydroxide paper, aluminum hydroxide paper, and magnesium silicate paper. Papers such as, or inorganic fiber non-woven fabrics such as glass fiber non-woven fabrics are preferable, and these may be mixed (or laminated) and used.
- inexpensive papers that can be discarded after the peeling are preferable. These surface materials are usually provided in the form of rolls.
- a material kneaded with an additive such as a flame retardant may be used as the flexible surface material.
- an additive such as a flame retardant
- Various methods can be used to bond the surface material to the phenol resin foam, and an adhesive such as epoxy resin may be used, but in terms of manufacturing cost and prevention of complication of the manufacturing process. From the surface as well, it is preferable that the phenol resin foam is solely due to the adhesive force when the surface material is thermally cured.
- the exudation rate from the surface material can be evaluated by the measurement method described later, but it is 30% or less. It is preferably 25% or less, more preferably 20% or less, still more preferably 15% or less, and most preferably 10% or less. When it is 30% or less, a phenol resin foam laminated board having a good appearance can be obtained, and the surface material peeling strength at a 45 ° angle is also low, so that the surface material can be peeled off and used as a phenol resin foam. Become.
- the surface material peeling strength of the phenolic resin foam laminated plate of the present embodiment at a 45 ° angle is preferably 1,000 g or less, more preferably 900 g or less, still more preferably 800 g or less, and most preferably. Is 700 g or less.
- the surface material peeling strength of the phenol resin foam laminated board at a 45 ° angle is 1,000 g or less, the surface material can be easily peeled off and can be easily used without the surface material.
- the face material peeling strength at a 45 ° angle is the amount of HCFO-1224yd (Z) added, the amount of solid foam nucleating agent used and added, the mass average molecular weight of the phenol resin, and the foamable phenol resin composition. It can be adjusted to a desired value by changing the temperature or the like.
- the surface material peeling strength of the phenol resin foam laminated board at a 45 ° angle can be measured by the method described in the examples of the present specification.
- the method for producing the phenol resin foam laminate includes a mixing step of mixing the above-mentioned foamable phenol resin composition with a mixer, a discharge step of discharging the mixed foamable phenol resin composition onto the lower surface material, and a discharge step of discharging the mixed foamable phenol resin composition onto the lower surface material. It is possible to adopt a continuous production method including a foam laminate manufacturing process for producing a phenol resin foam laminate from the phenol resin composition discharged onto the lower surface material.
- the phenol resin composition discharged onto the lower surface material is coated with the upper surface material, and then preformed so as to be leveled from the vertical direction while being foamed and cured, and then foaming and curing are carried out. This is finally molded into a plate shape.
- a method of using a slat type double conveyor As a method of preforming or main forming, a method of using a slat type double conveyor, a method of using a metal roll or a steel plate, a method of using a plurality of these in combination, and the like are used for manufacturing purposes.
- Various methods can be mentioned according to the above.
- the effervescent phenol resin composition coated with the upper and lower surface materials is continuously guided into the slat type double conveyor and then heated. It can be foamed and cured to form a plate while adjusting the thickness to a predetermined value by applying pressure from the vertical direction.
- the temperature of the effervescent phenol resin composition when discharged onto the lower surface material is preferably 35 ° C. or higher and 45 ° C. or lower.
- the temperature of the effervescent phenol resin composition is 35 ° C. or higher, the effervescent phenol resin composition tends to foam in the initial stage, so that the exudation of the effervescent phenol resin composition from the lower surface material is suppressed. It will be easier.
- the temperature of the effervescent phenol resin composition is 45 ° C. or lower, it becomes easy to suppress the emission of HCFO-1224yd (Z), which is a foaming agent having a low boiling point.
- the temperature of the effervescent phenol resin composition discharged onto the lower surface material can be adjusted by adjusting the temperature control temperature and flow rate of the mixing head for mixing the various compositions, the flow rate, and the like.
- the step of preforming from the upper surface material while foaming and curing the foamable phenol resin composition discharged onto the lower surface material is preferably 40 ° C. or higher and 80 ° C. or lower.
- the temperature is 40 ° C. or higher, the effect of promoting foaming in the preforming step can be easily obtained, and curing can be promoted.
- the temperature is 80 ° C. or lower, it is less likely to be affected by internal heat generation in the vicinity of the central portion in the thickness direction, the central portion temperature is less likely to rise, and a decrease in the closed cell ratio can be suppressed.
- the heating temperature control condition of the main molding step following the premolding step is 65 ° C. or higher and 100 ° C. or lower.
- the main molding can be performed using an endless steel belt type double conveyor, a slat type double conveyor, a roll or the like.
- the residence time of this molding step is preferably 5 minutes or more and 2 hours or less because it is the main step of causing the foaming and curing reactions.
- the residence time is 5 minutes or more, foaming and curing can be sufficiently promoted.
- the residence time is 2 hours or less, the production efficiency of the phenol resin foam laminated board can be improved.
- it is desirable that the temperature difference between the upper and lower conveyors is less than 4 ° C.
- the post-curing step is applied.
- the temperature of the post-curing step is preferably 90 ° C. or higher and 120 ° C. or lower.
- the temperature is 90 ° C. or higher, the moisture in the foam plate is easily dissipated, and when the temperature is 120 ° C. or lower, a decrease in the closed cell ratio of the product can be suppressed and high heat insulating performance can be exhibited.
- the moisture in the effervescent phenol resin composition can be dissipated after the final molding.
- This reaction solution was concentrated at 60 ° C. to obtain phenol resin A.
- the mass average molecular weight of the phenol resin A and the viscosity at 40 ° C. were measured by the following methods, the mass average molecular weight was 1,300 and the viscosity at 40 ° C. was 9,700 mPa ⁇ s.
- Measurement condition Measuring device: Shodex System21 (manufactured by Showa Denko KK) Column: Shodex asahipak GF-310HQ (7.5 mm ID x 30 cm) Eluent: 0.1% by mass of lithium bromide was dissolved in N, N dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) and used.
- Example 1 ⁇ Manufacturing method of phenol resin foam laminated board> (Example 1) 3.0 parts by mass of a composition containing 50% each of a block copolymer of ethylene oxide-propylene oxide and polyoxyethylene dodecylphenyl ether as a surfactant with respect to 100 parts by mass of phenol resin A. Mixed with. This is used as a phenol resin composition. With respect to 100 parts by mass of the phenol resin composition containing the above surfactant, 4.0 parts by mass of phenol resin foam powder as a solid foam nucleating agent and 4.0 parts by mass of the phenol resin composition as a foaming agent, HCFO-1224yd (Z).
- the phenol resin foam powder used here is a phenol resin foam (neomafoam manufactured by Asahi Kasei Kenzai Co., Ltd.) crushed powder (average particle size) crushed by the same procedure as in Example 1 of JP-A-2008-024868.
- the volume was 28.0 ⁇ m and the bulk density was 181 kg / m 3 ), and the mixture was kneaded with the phenol resin composition in a twin-screw extruder before the addition of the foaming agent and the acidic curing agent. Then, a foaming agent and an acidic curing agent were mixed, and the obtained foaming phenol resin composition was distributed by a multi-port pipe and supplied onto a moving lower surface material.
- the mixer the one disclosed in Japanese Patent Application Laid-Open No. 10-225993 was used.
- the phenol resin composition containing the solid foam nucleating agent and the foaming agent introduction port are on the upper side surface of the mixer, and the acid curing agent introduction port is on the side surface near the center of the stirring part where the rotor stirs.
- the mixer provided was used. After the stirring part, it is connected to a nozzle for discharging the effervescent phenol resin composition. That is, the mixer is composed of a mixing section (first stage) up to the acid curing agent introduction port, a mixing section (second stage) from the acid curing agent introduction port to the stirring end section, and a distribution section from the stirring end section to the nozzle. There is.
- the distribution unit has a plurality of nozzles at the tip, and is designed so that the mixed effervescent phenol resin composition is uniformly distributed. Further, the distribution unit has a jacket type structure so that heat can be sufficiently exchanged by temperature control water, and the temperature control water temperature of the distribution unit is set to 23 ° C. Further, a thermocouple was installed at the discharge port of the multi-port distribution pipe so that the temperature of the foamable phenol resin composition could be detected, and the rotation speed of the mixing head was set to 300 rpm. At this time, the temperature of the effervescent phenol resin composition discharged onto the lower surface material was 39 ° C.
- the effervescent phenol resin composition supplied onto the lower surface material was introduced into a preforming step in which the temperature was adjusted to 65 ° C., and 30 seconds later, preforming was performed from above the upper surface material with a free roller.
- the preforming was adjusted by setting the roll to a height that was 2/3 of the floss height at the time of ejection. After that, it was introduced into a slat type double conveyor heated to 83 ° C. so as to be sandwiched between two surface materials (main molding step), cured with a residence time of 15 minutes, and then placed in an oven at 110 ° C. for 2 After time curing (post-curing step), a phenol resin foam laminated board having a thickness of 50 mm was obtained.
- polyester non-woven fabric As the surface material, polyester non-woven fabric (Asahi Kasei Corporation Ertus E05060, basis weight 60 g / m 2 ) was used for both the upper and lower surface materials.
- the characteristics of the obtained phenol resin foam and the phenol resin foam laminate (density of phenol resin foam, closed cell ratio, average cell diameter, space volume in phenol resin foam 22.4 ⁇ 10 -3 m 3).
- the content of HCFO-1224yd (Z) per per, the ratio of the exuded area from the surface material, the peeling strength of the surface material at a 45 ° angle, and the thermal conductivity in a 23 ° C environment) were evaluated by the following methods. did.
- the average cell diameter of phenol resin foam was measured by the following method with reference to the method described in JIS K6402. A scanning electron microscope was used to magnify the cut surface of the test piece obtained by cutting approximately the center of the phenolic resin foam laminate in the thickness direction parallel to the front and back surfaces with a scanning electron microscope. Draw four straight lines with a length of 90 mm (corresponding to 1,800 ⁇ m in the actual cross section of the foam) avoiding voids, and calculate the number of cells measured with each straight line according to the number of bubbles crossed by each straight line. The value obtained by dividing 1,800 ⁇ m by the average value thereof was taken as the average cell diameter.
- the surface material peeling strength of the phenol resin foam laminated board at a 45 ° angle was measured and determined as follows (see FIG. 1). First, the phenol resin foam laminated board is cut into a width of 50 mm and a length of 120 mm (the length direction coincides with the product flow direction), and one of the surface materials (a) and (b) located on the upper and lower surfaces. The surface material (b) was peeled off.
- the evaluation sample 1 having the surface material (a) having a width of 50 mm, a length of 120 mm, and a thickness of 25 mm is provided. Prepared. Next, a cutter was used to make a notch with a depth of 20 mm in the thickness direction from the side surface having no surface material (a) at a position 20 mm from one end in the length direction of the evaluation sample 1. At the cut position, the base material 2 of the evaluation sample was carefully divided in the thickness direction. At this time, no force was applied in the length direction so that the surface material (a) (corresponding to the surface material 3 in FIG.
- the surface material peel strength (a) was taken as the surface material peel strength (a).
- an evaluation sample having a surface material (b), a width of 50 mm, a length of 120 mm, and a thickness of 25 mm was prepared, and the surface material peel strength (b) was determined in the same manner as the surface material peel strength (a).
- the lower value of the surface material peeling strength (a) and the surface material peeling strength (b) was defined as the surface material peeling strength (unit: g) of the phenol resin foam laminated plate at a 45 ° angle.
- the detection sensitivity of the generated gas component was measured, and the composition ratio was calculated from the detection area area and the detection sensitivity of each gas component obtained by the above GC / MS.
- the GC / MS measurement was set and performed as follows.
- ⁇ Content of HCFO-1224yd (Z) in phenol resin foam A phenol resin foam laminated board sample is cut into a square of about 100 mm, 6 specimens are prepared, and 6 bags with a zipper (hereinafter abbreviated as a bag with a zipper) having heat resistance that can be sealed are prepared. The mass of the bag was measured with a precision balance. The sample was placed in a circulating oven whose temperature was adjusted to 70 ° C. for 24 ⁇ 0.5 hr to disperse the water contained therein, and then immediately placed in a bag with a zipper, sealed, and cooled to room temperature.
- a zipper hereinafter abbreviated as a bag with a zipper
- the water content at the time of measuring W1 and W2 in this test is WS1 and WS2 in the following formula (2), respectively.
- the difference between WS1 and WS2 is subtracted from the difference between W1 and W2, and the solid phenol resin density is calculated from the volume (V) of the specimen. It is defined as 1.3 g / cm 3 , which is a generally known density of phenolic resin, and the volume obtained by subtracting the resin volume calculated from W2 (space volume in the foam) and the density of air (0.00119 g).
- the air buoyancy mass (WF) calculated by (/ mL) was added, and the volatile component mass (W3) was measured.
- W3 was multiplied by the measured ratio in the measured HCFO-1224yd (Z) and other foaming gas components to calculate the mass (W4) of HCFO-1224yd (Z).
- W3 and WF are represented by the following formulas, respectively.
- W3 (W1-W2)-(WS1-WS2) + WF
- WF (V-W2 / 1.3) x 0.00119 (3)
- the content of HCFO-1224yd (Z) in the foam (mol / 22.4 ⁇ 10 -3 m 3 ) was calculated by using the molecular weight of HCFO-1224yd (Z).
- the phenol resin foam laminate was cut into 300 mm squares, and the specimen was placed in an atmosphere of 23 ⁇ 1 ° C. and humidity of 50 ⁇ 2%. Then, the change over time of the weight was measured every 24 hours, and the state was confirmed and adjusted until the change in weight after the elapse of 24 hours became 0.2% by mass or less.
- the state-adjusted foam laminate specimen was introduced into a thermal conductivity device also placed in an atmosphere of 23 ⁇ 1 ° C. and a humidity of 50 ⁇ 2%. If the thermal conductivity measuring device is not placed in a room controlled to 23 ⁇ 1% and humidity 50 ⁇ 2% where the foam laminate specimen was placed, the condition can be confirmed and the state can be checked in the above-mentioned atmosphere.
- the adjusted specimen was immediately placed in a polyethylene bag, the bag was closed, and the sample was taken out of the bag within 1 hour, and the thermal conductivity was measured promptly.
- the thermal conductivity measurement is performed under the conditions that the thermal conductivity at 23 ° C is a low temperature plate of 13 ° C and a high temperature plate of 33 ° C. ”) Was used.
- Example 2 A phenol resin foam laminated board was obtained in the same manner as in Example 1 except that the temperature control water temperature of the mixer distribution section was set to 16 ° C.
- Example 3 A phenol resin foam laminated board was obtained in the same manner as in Example 1 except that the temperature control water temperature of the mixer distribution section was set to 28 ° C.
- Example 4 A phenol resin foam laminated board was obtained in the same manner as in Example 1 except that phenol resin B was used instead of phenol resin A.
- Example 5 A phenol resin foam laminated board was obtained in the same manner as in Example 1 except that phenol resin C was used instead of phenol resin A.
- Example 6 A composition consisting of 7.6 parts by mass of a mixture of 65% by mass of HCFO-1224yd (Z) and 35% by mass of cyclopentane as a foaming agent and 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as an acidic curing agent.
- a phenol resin foam laminated plate was obtained in the same manner as in Example 1 except that 0 parts by mass was added.
- Example 7 A composition consisting of 7.7 parts by mass of a mixture of 40% by mass of HCFO-1224yd (Z) and 60% by mass of isopentane as a foaming agent and 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as an acidic curing agent is 13.2.
- a phenol resin foam laminated plate was obtained in the same manner as in Example 1 except that parts by mass were added.
- Example 8 A composition consisting of 8.3 parts by mass of a mixture of 40% by mass of HCFO-1224yd (Z) and 60% by mass of 2-chloropropane as a foaming agent and 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as an acidic curing agent was prepared.
- a phenol resin foam laminated plate was obtained in the same manner as in Example 1 except that 3 parts by mass was added.
- Example 9 9.7 parts by mass of a mixture of HCFO-1224yd (Z) 40% by mass, HCFO-1233zd (E) 35% by mass, and cyclopentane 25% by mass as a foaming agent, and 80% by mass of xylene sulfonic acid and diethylene glycol as an acidic curing agent.
- a phenol resin foam laminated board was obtained in the same manner as in Example 1 except that 13.5 parts by mass of a composition consisting of a 20% by mass mixture was added.
- Example 10 9.7 parts by mass of a mixture of HCFO-1224yd (Z) 40% by mass, HCFO-1233zd (E) 35% by mass and isopentane 25% by mass as a foaming agent, and xylene sulfonic acid 80% by mass and diethylene glycol 20 as an acidic curing agent.
- a phenol resin foam laminated board was obtained in the same manner as in Example 1 except that 13.6 parts by mass of a composition composed of a mass% mixture was added.
- Example 11 Example 1 and Example 1 except that aluminum hydroxide powder (manufactured by Tomoe Kogyo Co., Ltd., B-325, average particle size 23.0 ⁇ m) is added as a solid foam nucleating agent to the phenol resin composition in an amount of 3.0% by mass. In the same manner, a phenol resin foam laminate was obtained.
- aluminum hydroxide powder manufactured by Tomoe Kogyo Co., Ltd., B-325, average particle size 23.0 ⁇ m
- Example 12 A composition consisting of 7.9 parts by mass of a mixture of 85% by mass of HCFO-1224yd (Z) and 15% by mass of cyclopentane as a foaming agent and 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as an acidic curing agent.
- a phenol resin foam laminated plate was obtained in the same manner as in Example 1 except that 2 parts by mass was added.
- Example 2 As in Example 1, no solid foaming nucleating agent was used as the foaming nucleating agent, and nitrogen, which is a gas foaming nucleating agent, was added so as to be 1% by mass with respect to 100 parts by mass of the foaming agent. A phenol resin foam laminated board was obtained.
- Example 3 A phenol resin foam laminated board was obtained in the same manner as in Example 1 except that the temperature control water temperature of the mixer distribution section was 14 ° C.
- Example 4 A phenol resin foam laminated board was obtained in the same manner as in Example 1 except that the temperature control water temperature of the mixer distribution section was set to 30 ° C.
- Table 1 summarizes the characteristic production conditions of Examples 1 to 12 and Comparative Examples 1 to 4 and the characteristic evaluation results of the obtained phenol resin foam laminated board.
- the phenol resin foam laminates obtained in Examples 1 to 12 have a foaming agent in the laminate as compared with the phenol resin foam laminates obtained in Comparative Examples 1 to 4. It can be seen that while achieving low thermal conductivity without reducing the filling amount, the suppression of seepage into the laminated plate surface material is also satisfied.
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Abstract
Description
[2]炭素数6以下の脂肪族炭化水素および炭素数5以下の塩素化飽和炭化水素から選ばれるガス成分を少なくとも1つ含んでいる、[1]に記載のフェノール樹脂発泡体積層板。
[3]前記表面材が、不織布、織布、および紙類の何れかからなる、[1]又は[2]に記載のフェノール樹脂発泡体積層板。
[4]45°角度での表面材剥離強度が1,000g以下である、[1]~[3]のいずれかに記載のフェノール樹脂発泡体積層板。
[5]23℃環境下における熱伝導率が0.0185W/m・K以下である、[1]~[4]のいずれかに記載のフェノール樹脂発泡体積層板。
本実施形態におけるフェノール樹脂発泡体積層板(以下、「発泡体積層板」という場合がある。)は、硬化反応によって形成されたフェノール樹脂硬化体中に、多数の気泡が分散した状態で存在するフェノール樹脂発泡体と、当該フェノール樹脂発泡体の一面および当該一面の裏面の少なくとも一方に表面材とを備える積層体である。なお、本実施形態の発泡体積層板は、表面材からの発泡性フェノール樹脂組成物の浸み出しが少なく、上下の表面材を剥離することが可能であることから、表面材を剥離してなる母材の状態で、難燃性および断熱性に優れる建材などとして使用することもできる。なお、本実施形態における「厚み方向」とは、発泡体積層板の三辺のうち最も短い辺の寸法を指し、通常、発泡体積層板の製造時に下表面材上の発泡性フェノール樹脂組成物が発泡して成長する方向である。
本実施形態のフェノール樹脂発泡体積層板のフェノール樹脂発泡体の密度は、20kg/m3以上55kg/m3以下であり、好ましくは22kg/m3以上50kg/m3以下であり、より好ましくは24kg/m3以上45kg/m3以下であり、さらに好ましくは26kg/m3以上40kg/m3以下であり、最も好ましくは、26kg/m3以上36kg/m3以下である。密度が20kg/m3以上であると圧縮強度、および曲げ強さ等の機械的強度が確保でき、発泡体の取り扱い時に破損が起こることを回避することができる。一方、密度が55kg/m3以下であると、樹脂部の伝熱が増大しにくいため、断熱性能を保つことができる。なお、フェノール樹脂発泡体の密度はフェノール樹脂発泡体への発泡剤の充填割合を調整すればよく、主に、フェノール樹脂発泡体への発泡剤の仕込み割合、発泡性フェノール樹脂組成物の温度、混合した発泡性フェノール樹脂組成物を下表面材上に吐出する工程における予成形のタイミング、さらには、発泡剤の添加量と酸性硬化剤として用いられる有機酸の添加量との比、温度や滞留時間等の硬化条件などの変更により所望の値に調整できる。
次に、上述したフェノール樹脂発泡体積層板の製造方法について説明する。
反応器に52質量%ホルムアルデヒド水溶液(52質量%ホルマリン)3,500kgと99質量%フェノール2,510kg(不純物として水を含む)とを仕込み、プロペラ回転式の攪拌機により攪拌し、温調機により反応器内部液温度を40℃に調整した。次いで48質量%水酸化ナトリウム水溶液を加えながら昇温して、反応を行わせた。反応液のオストワルド粘度が110センチストークス(=110×10-6m2/s、25℃における測定値)に到達した段階で、反応液を冷却し、尿素を398kg添加した。その後、反応液を30℃まで冷却し、パラトルエンスルホン酸一水和物の50質量%水溶液でpHを6.4に中和した。
回転粘度計(東機産業(株)製、R-100型、ローター部は3°×R-14)を用い、40℃で3分間安定させた後の測定値をフェノール樹脂Aの粘度とした。
ゲル浸透クロマトグラフィー(GPC)測定により以下のような条件で測定を行い、後に示す標準物質(標準ポリスチレン、2-ヒドロキシベンジルアルコールおよびフェノール)によって得られた検量線よりフェノール樹脂の質量平均分子量Mwを求めた。
前処理:
フェノール樹脂約10mgをN,Nジメチルホルムアミド(和光純薬工業株式会社製、高速液体クロマトグラフ用)1mlに溶解し、0.2μmメンブレンフィルターでろ過したものを測定溶液として用いた。
測定条件:
測定装置:Shodex System21(昭和電工株式会社製)
カラム:Shodex asahipak GF-310HQ(7.5mmI.D.×30cm)
溶離液:臭化リチウム0.1質量%をN,Nジメチルホルムアミド(和光純薬工業株式会社製、高速液体クロマトグラフ用)に溶解し使用した。
流量:0.6ml/分
検出器:RI検出器
カラム温度:40℃
標準物質:標準ポリスチレン(昭和電工株式会社製「Shodex standard SL-105」)、2-ヒドロキシベンジルアルコール(シグマアルドリッチ社製、99%品)、フェノール(関東化学株式会社製、特級)
反応液のオストワルド粘度が80センチストークス(=80×10-6m2/s、25℃における測定値)に到達した段階で、反応液を冷却し、尿素を430kg添加した以外は、フェノール樹脂Aと同様の手順で合成し、反応液の濃縮条件を調整することで、質量平均分子量が900、40℃における粘度が9,800mPa・sである、フェノール樹脂Bを得た。
反応液のオストワルド粘度が240センチストークス(=160×10-6m2/s、25℃における測定値)に到達した段階で、反応液を冷却し、尿素を310kg添加した以外は、フェノール樹脂Aと同様の手順で合成し、反応液の濃縮条件を調整することで、質量平均分子量が2,500、40℃における粘度が9,300mPa・sである、フェノール樹脂Cを得た。
反応液のオストワルド粘度が75センチストークス(=75×10-6m2/s、25℃における測定値)に到達した段階で、反応液を冷却し、尿素を450kg添加した以外は、フェノール樹脂Aと同様の手順で合成し、反応液の濃縮条件を調整することで、質量平均分子量が800、40℃における粘度が9,500mPa・sである、フェノール樹脂Dを得た。
(実施例1)
フェノール樹脂A100質量部に対して、界面活性剤としてエチレンオキサイド-プロピレンオキサイドのブロック共重合体とポリオキシエチレンドデシルフェニルエーテルを質量比率でそれぞれ50%ずつ含有する組成物を3.0質量部の割合で混合した。これをフェノール樹脂組成物とする。上記界面活性剤を含むフェノール樹脂組成物100質量部に対して、固体発泡核剤としてフェノール樹脂発泡体粉をフェノール樹脂組成物に対して4.0質量部、発泡剤としてHCFO-1224yd(Z)40質量%とシクロペンタン60質量%の混合物7.2質量部、さらに、酸性硬化剤としてキシレンスルホン酸80質量%とジエチレングリコール20質量%の混合物からなる組成物を12.0質量部添加し、18℃に温調した回転数可変式のミキシングヘッドに供給した。なお、ここで用いたフェノール樹脂発泡体粉は、特開2008-024868号の実施例1と同様の手順で粉砕した、フェノール樹脂発泡体(旭化成建材(株)製ネオマフォーム)粉砕粉(平均粒径は28.0μm、嵩密度は181kg/m3)であり、発泡剤および酸性硬化剤の添加前に、二軸押出機にてフェノール樹脂組成物と混練した。その後、発泡剤および酸性硬化剤を混合し、得られた発泡性フェノール樹脂組成物をマルチポート分配管にて分配し、移動する下表面材上に供給した。なお、混合機(ミキサー)は、特開平10-225993号に開示されたものを使用した。即ち、混合機の上部側面に、固体発泡核剤を含むフェノール樹脂組成物、および、発泡剤の導入口があり、回転子が攪拌する攪拌部の中央付近の側面に酸性硬化剤の導入口を備えている混合機を使用した。攪拌部以降は発泡性フェノール樹脂組成物を吐出するためのノズルに繋がっている。即ち、混合機は、酸性硬化剤導入口までを混合部(前段)、酸性硬化剤導入口~攪拌終了部を混合部(後段)、攪拌終了部~ノズルを分配部とし、これらにより構成されている。分配部は先端に複数のノズルを有し、混合された発泡性フェノール樹脂組成物が均一に分配されるように設計されている。さらに、分配部はジャケット式構造になっており、温調水により十分熱交換できるようになっており、分配部の温調水温度を23℃に設定した。また、マルチポート分配管の吐出口には、発泡性フェノール樹脂組成物の温度を検出できるように熱電対が設置してあり、ミキシングヘッドの回転数を300rpmに設定した。このときの下表面材上に吐出した発泡性フェノール樹脂組成物の温度は39℃であった。下表面材上に供給した発泡性フェノール樹脂組成物は、65℃に温調された予成形工程に導入され、30秒後に、上表面材上方より、フリーローラーにて予成形を行った。予成形は、吐出時のフロス高さの2/3となる高さにロールをセットし調節した。その後、二枚の表面材で挟み込まれるようにして、83℃に加熱されたスラット型ダブルコンベアに導入され(本成形工程)、15分の滞留時間で硬化させた後、110℃のオーブンで2時間キュアさせ(後硬化工程)、厚み50mmのフェノール樹脂発泡体積層板を得た。なお、表面材としては、上下表面材ともに、ポリエステル不織布(旭化成(株)エルタスE05060、目付量60g/m2)を使用した。
200mm角のフェノール樹脂発泡体積層板を試料とし、この試料から表面材を取り除いた後、JIS K7222に従い質量と見かけ容積を測定して求めた。
ASTM-D-2856(C法)に従い測定した。具体的には、フェノール樹脂発泡体積層板より表面材を取り除いた後、直径35mm~36mmの円柱形試料をコルクボーラーで刳り貫き、高さ30mm~40mmに切り揃えた後、空気比較式比重計(東京サイエンス社製、1,000型)の標準使用方法により試料容積を測定した。その試料容積から、試料質量とフェノール樹脂硬化体の密度から計算した壁(気泡やボイド以外の部分)の容積を差し引いた値を、試料の外寸から計算した見かけの容積で割った値を独立気泡率とした。ここで、フェノール樹脂硬化体の密度は1.3kg/Lとした。
平均気泡径は、JIS K6402に記載の方法を参考に、以下の方法で測定した。フェノール樹脂発泡体積層板の厚み方向のほぼ中央を表裏面に平行に切削して得た試験片の切断面を50倍に拡大した走査型電子顕微鏡で写真を撮影し、得られた写真上にボイドを避けて90mmの長さ(実際の発泡体断面における1,800μmに相当する)の直線を4本引き、各直線が横切った気泡の数に準じて測定したセル数を各直線で求め、それらの平均値で1,800μmを割った値を平均気泡径とした。
フェノール樹脂発泡体積層板の上下表面材上の発泡性フェノール樹脂樹脂組成物が浸み出した箇所をペンで囲んで印を付けた後、該フェノール樹脂発泡体積層板の300mm×300mmエリアをデジタルカメラで撮影し、色調補正後、ピクセルカウンターソフトにて樹脂組成物が浸み出した箇所の画素数と300mm×300mmエリア全体の画素数をそれぞれカウントし、下記計算式(1)にて浸み出し面積割合を算出した。
表面材からの浸み出し面積割合(%)=(囲んだ部分の画素数/300mm×300mmエリア全体の画素数)×100 (1)
フェノール樹脂発泡体積層板の45°角度での表面材剥離強度は以下の様に測定して求めた(図1参照)。先ず、フェノール樹脂発泡体積層板を、幅50mm、長さ120mm(長さ方向が製品流れ方向と一致する)に切り出し、上下面に位置する表面材(a)、(b)のうちの一方の表面材(b)を剥離した。その後、表面材(b)剥離後のフェノール樹脂発泡体積層板を上下面と平行方向に切断することで、表面材(a)を備えた幅50mm、長さ120mm、厚み25mmの評価用サンプル1を準備した。次に、評価用サンプル1の長さ方向の一端から20mmの位置に、カッターを用いて、表面材(a)を有さない側の面から厚み方向に深さ20mmの切り込みを入れた。その切込み位置にて、評価用サンプルの母材2を厚み方向に慎重に分割した。この際に表面材(a)(図1中の表面材3に相当)が母材2から剥がれないように長さ方向の力を加えないようにした。そして、母材が分割された評価用サンプル1の、母材の長さが長い側の部位を、図1のようにクランプ7で水平面と45°の角度になるように保持し、また、母材の長さが短い側の部位の先に金属ワイヤ5で繋がれた容器6を、ペーパークリップ4を介してセットした。その後、ポンプ(図示せず)を用いて空の容器6内に、100g/分の投入速度で、水を連続的に投入した。表面材3が評価用サンプル1の長さ方向に、切り込み位置から50mm剥離した時点での容器6内の水の質量を測定した。同様の操作を二回行い、ペーパークリップ4、金属ワイヤ5、容器6、および得られた水の質量の合計の平均値を表面材剥離強度(a)とした。さらに別途、表面材(b)を備え、幅50mm、長さ120mm、厚み25mmの評価用サンプルを準備し、表面材剥離強度(a)と同様にして表面材剥離強度(b)を求めた。そして、表面材剥離強度(a)および表面材剥離強度(b)のうち低い方の値を、フェノール樹脂発泡体積層板の45°角度での表面材剥離強度(単位:g)とした。
ボートタイプ水分気化装置を有するカールフィッシャー水分計で、110℃で加熱して気化させた水分を測定した。
表面材を剥がした発泡体試料を10gと金属製やすりを10L容器(製品名テドラーバック)に入れて密封し、窒素5Lを注入した。テドラーバックの上からヤスリを使い試料を削り、細かく粉砕した。続いて、81℃に温調された温調機内に10分間入れた。テドラーバック中で発生したガスを100μL採取し、GC/MSで測定し、発生したガス成分の種類と組成比を分析した。なお、発泡ガスの種類は、保持時間とマススペクトルから同定を行った。別途、発生したガス成分の検出感度を測定し、上記GC/MSで得られた各ガス成分の検出エリア面積と検出感度より、組成比を算出した。
(GC/MS条件)
GC/MSの測定は以下のように設定し、行った。
ガスクロマトグラフィー:アジレント・テクノロジー社製「Agilent7890型」
カラム:DB-5MS(0.25mmφ×30m、膜厚1μm)
キャリアガス:ヘリウム
流量:1ml/分
注入口の温度:150℃
注入方法:スプリット法(1/10)
試料の注入量:溶液1μL(気体試料の場合はガスタイトシリンジを用いて100μl)
カラム温度:40℃(5分)の後、50℃/minで150℃まで昇温し、4.8分保持 質量分析:日本電子株式会社製「Q1000GC型」
イオン化方法:電子イオン化法(70eV)
スキャン範囲:m/Z=10~500
電圧:-1,300V
イオン源温度:230℃
インターフェース温度:150℃
フェノール樹脂発泡体積層板サンプルを約100mm角に切断し、試片6個を準備すると共に、密封可能な耐熱性を有するチャック付袋(以下チャック付袋と略す)を6袋準備し、各々の袋の質量を精密天秤で、測定した。試片を70℃に温調された循環式オーブン内に24±0.5hr入れ含有する水分を飛散させた後、速やかに、チャック付袋に入れ、封をして、室温まで冷やした。室温まで冷却後、チャック付袋より試片を取り出し、速やかに試片の表面材を剥離すると共に、各試片の質量(W1)を精密天秤より測定すると共に、各辺の長さをノギスにより測定し、試片の体積(V)を算出した。その後、各試片をチャック付袋に戻し、一部の開口部を残し、室温の油圧プレスの盤面間に入れ、油圧プレスで約200N/cm2の圧力まで徐々に圧縮し、試片の気泡を破壊した。6試片の内の3試片について、試片の一部試料を採取し、前記固形物中の水分量の測定法により、含有する水分量を測定し、3点を平均した水分量(WS1)を求めた。上記水分量測定のために一部採取した3試片の残り、および、それ以外の3試片について、引き続き、一部の開口部を残した試片入りチャック付袋内に収めたまま、81℃に温調された循環式オーブン内に30±5分入れた。その後、直ちに、粉体が袋から出ないようにしつつ袋内気体を排出し、袋を密封し、室温まで冷やした。室温まで冷却後、上記で水分率測定用試料採取を行っていない、試片入りチャック付袋の質量を精密天秤で測定し、チャック付袋の質量を差し引き、揮発成分が除かれた質量(W2)を3点測定した。同時に、上記で水分率測定用試料採取を行った3試片の袋より、さらに一部試料を採取し、同様に水分量を測定し、3点を平均した水分量(WS2)を求めた。すなわち、本試験における、W1、W2計測時の各水分量は、各々、下記式(2)中のWS1、および、WS2となる。
W3、WFは各々下記式で示される。
W3=(W1-W2)-(WS1-WS2)+WF (2)
WF=(V-W2/1.3)×0.00119 (3)
発泡体中のHCFO-1224yd(Z)の含有量(mol/22.4×10-3m3)は、HCFO-1224yd(Z)の分子量を用いることにより算出した。
JIS A 1412-2:1999に準拠し、以下の方法で23℃の環境下におけるフェノール樹脂発泡体積層板の厚み方向の熱伝導率を測定した。具体的な手順は以下の通りである。
混合機分配部の温調水温度を16℃とする以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
混合機分配部の温調水温度を28℃とする以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
フェノール樹脂Aの代わりに、フェノール樹脂Bを使用する以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
フェノール樹脂Aの代わりに、フェノール樹脂Cを使用する以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
発泡剤としてHCFO-1224yd(Z)65質量%とシクロペンタン35質量%の混合物7.6質量部、酸性硬化剤としてキシレンスルホン酸80質量%とジエチレングリコール20質量%の混合物からなる組成物を13.0質量部添加する以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
発泡剤としてHCFO-1224yd(Z)40質量%とイソペンタン60質量%の混合物7.7質量部、酸性硬化剤としてキシレンスルホン酸80質量%とジエチレングリコール20質量%の混合物からなる組成物を13.2質量部添加する以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
発泡剤としてHCFO-1224yd(Z)40質量%と2-クロロプロパン60質量%の混合物8.3質量部、酸性硬化剤としてキシレンスルホン酸80質量%とジエチレングリコール20質量%の混合物からなる組成物を13.3質量部添加する以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
発泡剤としてHCFO-1224yd(Z)40質量%、HCFO-1233zd(E)35質量%、および、シクロペンタン25質量%の混合物9.7質量部、酸性硬化剤としてキシレンスルホン酸80質量%とジエチレングリコール20質量%の混合物からなる組成物を13.5質量部添加する以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
発泡剤としてHCFO-1224yd(Z)40質量%、HCFO-1233zd(E)35質量%、および、イソペンタン25質量%の混合物9.7質量部、酸性硬化剤としてキシレンスルホン酸80質量%とジエチレングリコール20質量%の混合物からなる組成物を13.6質量部添加する以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
固体発泡核剤として水酸化アルミニウム粉末(巴工業(株)製、B-325、平均粒径23.0μm)をフェノール樹脂組成物に対して3.0質量%添加する以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
発泡剤としてHCFO-1224yd(Z)85質量%とシクロペンタン15質量%の混合物7.9質量部、酸性硬化剤としてキシレンスルホン酸80質量%とジエチレングリコール20質量%の混合物からなる組成物を13.2質量部添加する以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
フェノール樹脂Aの代わりに、フェノール樹脂Dを使用する以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
発泡核剤として、固体発泡核剤を使用せず、気体発泡核剤である窒素を発泡剤100質量部に対して1質量%となるように添加した以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
混合機分配部の温調水温度を14℃とする以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
混合機分配部の温調水温度を30℃とする以外は、実施例1と同様にして、フェノール樹脂発泡体積層板を得た。
2 評価用サンプルのフォーム部
3 評価用サンプルの下表面材
4 ペーパークリップ
5 金属ワイヤ
6 容器
7 クランプ
Claims (5)
- フェノール樹脂発泡体の一面および当該一面の裏面の少なくとも一方に可撓性の表面材が配されたフェノール樹脂発泡体積層板であって、前記フェノール樹脂発泡体は、HCFO-1224yd(Z)を含有し、密度が20kg/m3以上55kg/m3以下、独立気泡率が80%以上、平均気泡径が60μm以上200μm以下、前記表面材からの浸み出し面積割合が30%以下であり、かつ、前記フェノール樹脂発泡体内の空間体積22.4×10-3m3あたり、HCFO-1224yd(Z)の含有量が0.06mol以上0.35mol以下である、フェノール樹脂発泡体積層板。
- 炭素数6以下の脂肪族炭化水素および炭素数5以下の塩素化飽和炭化水素から選ばれるガス成分を少なくとも1つ含んでいる、請求項1に記載のフェノール樹脂発泡体積層板。
- 前記表面材が、不織布、織布、および紙類の何れかからなる、請求項1又は2に記載のフェノール樹脂発泡体積層板。
- 45°角度での表面材剥離強度が1,000g以下である、請求項1~3のいずれか1項に記載のフェノール樹脂発泡体積層板。
- 23℃環境下における熱伝導率が0.0185W/m・K以下である、請求項1~4のいずれか1項に記載のフェノール樹脂発泡体積層板。
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EP4101633A1 (en) | 2022-12-14 |
JP7223201B1 (ja) | 2023-02-15 |
CN114981084A (zh) | 2022-08-30 |
EP4101633A4 (en) | 2023-07-05 |
KR20220104037A (ko) | 2022-07-25 |
AU2021217298A1 (en) | 2022-09-01 |
US11932733B2 (en) | 2024-03-19 |
JPWO2021157698A1 (ja) | 2021-08-12 |
JP7191255B2 (ja) | 2022-12-16 |
TW202136031A (zh) | 2021-10-01 |
CA3166680A1 (en) | 2021-08-12 |
US20230074052A1 (en) | 2023-03-09 |
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TWI764561B (zh) | 2022-05-11 |
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