JP5002792B2 - Polysaccharide-modified phenolic resin, production method of polysaccharide-modified phenolic resin, resin-coated sand, polysaccharide-modified phenolic resin carbonized material, conductive resin composition, carbon material for electrode, electrode for secondary battery, electric double layer capacitor polarizability electrode - Google Patents
Polysaccharide-modified phenolic resin, production method of polysaccharide-modified phenolic resin, resin-coated sand, polysaccharide-modified phenolic resin carbonized material, conductive resin composition, carbon material for electrode, electrode for secondary battery, electric double layer capacitor polarizability electrode Download PDFInfo
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- JP5002792B2 JP5002792B2 JP2006231297A JP2006231297A JP5002792B2 JP 5002792 B2 JP5002792 B2 JP 5002792B2 JP 2006231297 A JP2006231297 A JP 2006231297A JP 2006231297 A JP2006231297 A JP 2006231297A JP 5002792 B2 JP5002792 B2 JP 5002792B2
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- Prior art keywords
- polysaccharide
- resin
- phenolic resin
- modified phenolic
- electrode
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Polymers [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims description 63
- 239000005539 carbonized material Substances 0.000 title claims description 47
- 229920005989 resin Polymers 0.000 title claims description 42
- 239000011347 resin Substances 0.000 title claims description 42
- 239000004576 sand Substances 0.000 title claims description 26
- 239000003990 capacitor Substances 0.000 title claims description 19
- 239000003575 carbonaceous material Substances 0.000 title claims description 15
- 239000011342 resin composition Substances 0.000 title claims description 11
- 239000005011 phenolic resin Substances 0.000 claims abstract description 101
- 150000002989 phenols Polymers 0.000 claims abstract description 87
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 26
- 239000005017 polysaccharide Substances 0.000 claims abstract description 26
- 238000006482 condensation reaction Methods 0.000 claims abstract description 25
- 150000004676 glycans Chemical class 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 9
- 229920002472 Starch Polymers 0.000 claims description 22
- 235000019698 starch Nutrition 0.000 claims description 21
- 239000008107 starch Substances 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 150000001299 aldehydes Chemical class 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 229920001353 Dextrin Polymers 0.000 claims description 6
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- 239000011231 conductive filler Substances 0.000 claims description 6
- 235000019425 dextrin Nutrition 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
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- 229920002558 Curdlan Polymers 0.000 claims description 4
- 239000001879 Curdlan Substances 0.000 claims description 4
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 235000019316 curdlan Nutrition 0.000 claims description 4
- 229940078035 curdlan Drugs 0.000 claims description 4
- 235000019423 pullulan Nutrition 0.000 claims description 4
- 235000000346 sugar Nutrition 0.000 claims description 4
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- 239000000230 xanthan gum Substances 0.000 claims description 4
- 229940082509 xanthan gum Drugs 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 6
- 229920003987 resole Polymers 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- 238000005452 bending Methods 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- -1 p-substituted phenols Chemical class 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 229920001568 phenolic resin Polymers 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000004312 hexamethylene tetramine Substances 0.000 description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
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- 238000010304 firing Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
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- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 244000215068 Acacia senegal Species 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920000084 Gum arabic Polymers 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000010489 acacia gum Nutrition 0.000 description 3
- 239000000205 acacia gum Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
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- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical group OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
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- 238000010998 test method Methods 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical group O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
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- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- 235000010491 tara gum Nutrition 0.000 description 2
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- UYVWNPAMKCDKRB-UHFFFAOYSA-N 1,2,4,5-tetraoxane Chemical compound C1OOCOO1 UYVWNPAMKCDKRB-UHFFFAOYSA-N 0.000 description 1
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- PCNMALATRPXTKX-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(C)(O)C=C1 PCNMALATRPXTKX-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229940035034 maltodextrin Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Mold Materials And Core Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Conductive Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、でんぷんなどの多糖類で変性した多糖類変性フェノール樹脂及びその製造方法に関するものであり、またこの多糖類変性フェノール樹脂を用いたレジンコーテッドサンド、多糖類変性フェノール樹脂炭化材料、導電性樹脂組成物、電極用炭素材料に関するものであり、さらに多糖類変性フェノール樹脂から得た電極用炭素材料で形成される二次電池用電極、電気二重層キャパシタ用電極に関するものである。 The present invention relates to a polysaccharide-modified phenolic resin modified with a polysaccharide such as starch and a method for producing the same, and a resin-coated sand, a polysaccharide-modified phenolic resin carbonized material using the polysaccharide-modified phenolic resin, a conductive property, and the like. The present invention relates to a resin composition and an electrode carbon material, and further to an electrode for a secondary battery and an electrode for an electric double layer capacitor formed of an electrode carbon material obtained from a polysaccharide-modified phenol resin.
本出願人は従前に、セルロースとフェノール類とを反応させることによって、フェノール樹脂と同等の樹脂を得ることができることを見出している（特許文献１参照）。 The present applicant has previously found that a resin equivalent to a phenol resin can be obtained by reacting cellulose and phenols (see Patent Document 1).
特許文献１の発明は、セルロースの粉体とフェノール類とを酸の存在下で反応させたものであり、このように反応させて得たフェノール系樹脂はノボラック型に相当するものであって、ヘキサメチレンテトラミン等の硬化剤と混合して加熱することによって、硬化させることができるものである。 The invention of Patent Document 1 is obtained by reacting cellulose powder and phenols in the presence of an acid, and the phenolic resin obtained by reacting in this way corresponds to a novolak type, It can be cured by mixing with a curing agent such as hexamethylenetetramine and heating.
このように特許文献１のものは、反応を終了して得たフェノール系樹脂は自硬化性を有するものではなく、ヘキサメチレンテトラミン等の硬化剤を配合して使用する必要があり、用途が制限されることになる。
一方、本発明者は、セルロースの代わりに、セルロースと同じ多糖類を用いることを検討しているが、特許文献１と同様にして多糖類とフェノール類とを反応させた場合、分子量が小さく、同様に自硬化性を有する樹脂を得ることはできない。仮にフェノール類に対する多糖類の反応モル比を上げても分子量の増加はわずかであり、熱を加えただけで硬化反応して不溶不融になる樹脂を得ることはできない。このため、特許文献１のものと同様に用途が限定され、種々の用途に応用することができないという問題を有するものであった。 On the other hand, the present inventor is considering using the same polysaccharide as cellulose instead of cellulose, but when the polysaccharide and phenol are reacted in the same manner as in Patent Document 1, the molecular weight is small, Similarly, a resin having self-curing properties cannot be obtained. Even if the reaction molar ratio of polysaccharides to phenols is increased, the molecular weight increases only slightly, and a resin that becomes insoluble and infusible by curing reaction cannot be obtained just by applying heat. For this reason, the use is limited like the thing of patent document 1, and it had the problem that it cannot apply to various uses.
本発明は上記の点に鑑みてなされたものであり、多様な用途に用いることができる多糖類変性フェノール樹脂及びその製造方法を提供することを目的とするものであり、またこの多糖類変性フェノール樹脂を用いた、性能の高いレジンコーテッドサンド、多糖類変性フェノール樹脂炭化材料、導電性樹脂組成物、電極用炭素材料、二次電池用電極、電気二重層キャパシタ分極性電極を提供することを目的とするものである。 The present invention has been made in view of the above points, and aims to provide a polysaccharide-modified phenolic resin that can be used in various applications and a method for producing the same, and the polysaccharide-modified phenol. The purpose is to provide a resin-coated sand, a polysaccharide-modified phenol resin carbonized material, a conductive resin composition, a carbon material for an electrode, an electrode for a secondary battery, and an electric double layer capacitor polarizable electrode using a resin. It is what.
本発明の請求項１に係る多糖類変性フェノール樹脂の製造方法は、フェノール類と、アルデヒド類と、でんぷん糖、デキストリン、ザンサンガム、カードラン、プルラン、シクロアミロース、キチン、でんぷんから選ばれる多糖類とを、塩基性反応触媒の存在下で付加縮合反応させることを特徴とするものである。 The method for producing a polysaccharide-modified phenolic resin according to claim 1 of the present invention comprises a phenol, an aldehyde, a polysaccharide selected from starch sugar, dextrin, xanthan gum, curdlan, pullulan, cycloamylose, chitin, and starch. Is subjected to an addition condensation reaction in the presence of a basic reaction catalyst .
この発明によれば、フェノール類とアルデヒド類及び多糖類を反応させることによって、レゾール型の多糖類変性フェノール樹脂を得ることができるものであり、加熱することによって不溶不融状態にすることができ、多様な用途に用いることができるものである。そして、多糖類変性フェノール樹脂の硬化物は柔軟性が発現して衝撃に強いという特性を有し、またこれを加熱すると容易に熱分解をして脆くなって急激に強度を低下させることができるという特性を有し、さらに酸素のない雰囲気で加熱すると炭化物収率が下がって炭化物の比表面積を増加させることができるという特性を有するものであり、これらの特性を利用した多用な用途に用いることができるものである。 According to the present invention, a resole-type polysaccharide-modified phenol resin can be obtained by reacting phenols with aldehydes and polysaccharides, and can be brought into an insoluble and infusible state by heating. It can be used for various purposes. The cured product of the polysaccharide-modified phenolic resin has a characteristic that it exhibits flexibility and is resistant to impact, and when heated, it can be easily pyrolyzed to become brittle and rapidly reduce its strength. In addition, when heated in an oxygen-free atmosphere, the carbide yield decreases and the specific surface area of the carbide can be increased, and it can be used for various applications utilizing these characteristics. It is something that can be done.
また請求項２の発明は、請求項１において、付加縮合反応を分散剤の存在下、攪拌しながら行なうことを特徴とするものである。 The invention of claim 2 is characterized in that, in claim 1, the addition condensation reaction is carried out in the presence of a dispersing agent with stirring.
この発明によれば、球状の粒子の形態に多糖類変性フェノール樹脂を調製することができるものである。 According to this invention, the polysaccharide-modified phenol resin can be prepared in the form of spherical particles.
また請求項３の発明は、請求項１又は２において、付加縮合反応を、生成される多糖類変性フェノール樹脂が熱硬化性を有する状態で停止することを特徴とするものである。 The invention of claim 3 is characterized in that, in claim 1 or 2, the addition condensation reaction is stopped in a state where the produced polysaccharide-modified phenol resin has thermosetting properties.
この発明によれば、未硬化であって熱を加えることによって硬化する状態に多糖類変性フェノール樹脂を調製することができ、成形材料やバインダーなどとして使用することができるものである。 According to this invention, the polysaccharide-modified phenol resin can be prepared in a state of being uncured and cured by applying heat, and can be used as a molding material or a binder.
また請求項４の発明は、請求項１又は２において、付加縮合反応を、生成される多糖類変性フェノール樹脂が不溶不融状態になるまで継続した後に停止することを特徴とするものである。 The invention of claim 4 is characterized in that, in claim 1 or 2, the addition condensation reaction is continued after the produced polysaccharide-modified phenol resin is in an insoluble and infusible state.
この発明によれば、得られた多糖類変性フェノール樹脂は硬化した状態にあるので、多糖類変性フェノール樹脂をフィラーなどとして使用することができるものである。 According to this invention, since the obtained polysaccharide-modified phenol resin is in a cured state, the polysaccharide-modified phenol resin can be used as a filler or the like.
本発明の請求項５に係る多糖類変性フェノール樹脂は、上記の請求項３に記載の製造方法で得られたことを特徴とするものである。 The polysaccharide-modified phenol resin according to claim 5 of the present invention is obtained by the production method according to claim 3 .
この発明によれば、得られた多糖類変性フェノール樹脂を上記のように成形材料やバインダーなど多様な用途に用いることができるものである。 According to this invention, the obtained polysaccharide-modified phenol resin can be used for various uses such as molding materials and binders as described above.
また本発明の請求項６に係る多糖類変性フェノール樹脂は、上記の請求項４に記載の製造方法で得られたことを特徴とするものである。 The polysaccharide-modified phenolic resin according to claim 6 of the present invention is obtained by the production method according to claim 4 .
この発明によれば、得られた多糖類変性フェノール樹脂を上記のようにフィラーなど多様な用途に用いることができるものである。 According to this invention, the obtained polysaccharide-modified phenol resin can be used for various uses such as a filler as described above.
また請求項７の発明は、請求項５の多糖類変性フェノール樹脂を加熱処理して不溶不融状態にしたことを特徴とするものである。
また請求項８の発明は、請求項５乃至７のいずれかにおいて、多糖類の含有量が１．０〜６０質量％であることを特徴とするものである。
The invention of claim 7 is characterized in that the polysaccharide-modified phenolic resin of claim 5 is heat-treated into an insoluble and infusible state.
The invention of claim 8 is characterized in that, in any of claims 5 to 7, the content of polysaccharide is 1.0 to 60% by mass.
この発明によれば、多糖類変性フェノール樹脂に、多糖類変性による特性を必要且つ十分に与えることができるものである。 According to the present invention, the polysaccharide-modified phenol resin can be given necessary and sufficient characteristics due to polysaccharide modification.
本発明の請求項９に係るレジンコーテッドサンドは、請求項５に記載の多糖類変性フェノール樹脂が、耐火骨材の表面にコーティングされたものであることを特徴とするものである。 The resin-coated sand according to claim 9 of the present invention is characterized in that the polysaccharide-modified phenolic resin according to claim 5 is coated on the surface of a refractory aggregate.
この発明によれば、レジンコーテッドサンドの多糖類変性フェノール樹脂をバインダーとして、鋳型を成形する用途に使用することができるものである。 According to the present invention, the resin-coated sand polysaccharide-modified phenol resin can be used as a binder for molding a mold.
本発明の請求項１０に係る多糖類変性フェノール樹脂炭化材料は、請求項６又は７に記載の多糖類変性フェノール樹脂が、非酸化性雰囲気下で熱処理して炭化されたものであることを特徴とするものである。 The polysaccharide-modified phenolic resin carbonized material according to claim 10 of the present invention is characterized in that the polysaccharide-modified phenolic resin according to claim 6 or 7 is carbonized by heat treatment in a non-oxidizing atmosphere. It is what.
この発明によれば、多糖類変性フェノール樹脂を炭化して炭化材料とすることによって、導電性フィラーや、電極材料などの用途に使用することができるものである。 According to the present invention, the polysaccharide-modified phenol resin is carbonized to form a carbonized material, which can be used for applications such as conductive fillers and electrode materials.
本発明の請求項１１に係る導電性樹脂組成物は、請求項１０に記載の多糖類変性フェノール樹脂炭化材料を、導電性フィラーとして樹脂に配合して成ることを特徴とするものである。 A conductive resin composition according to an eleventh aspect of the present invention is characterized in that the polysaccharide-modified phenolic resin carbonized material according to the tenth aspect is blended with a resin as a conductive filler.
この発明によれば、多糖類変性フェノール樹脂炭化材料を導電性フィラーとして用いて、導電性に優れた成形品などを成形することができるものである。 According to the present invention, it is possible to mold a molded article having excellent conductivity using a polysaccharide-modified phenol resin carbonized material as a conductive filler.
本発明の請求項１２に係る二次電池用電極は、請求項１０に記載の多糖類変性フェノール樹脂炭化材料を電極材料として形成されたことを特徴とするものである。 An electrode for a secondary battery according to a twelfth aspect of the present invention is formed using the polysaccharide-modified phenol resin carbonized material according to the tenth aspect as an electrode material.
この発明によれば、多糖類変性フェノール樹脂炭化材料を用いて電極特性の優れた電極を形成することができるものである。 According to this invention, an electrode excellent in electrode characteristics can be formed using a polysaccharide-modified phenol resin carbonized material.
本発明の請求項１３に係る電極用炭素材料は、請求項１０に記載の多糖類変性フェノール樹脂炭化材料が賦活処理されたものであることを特徴とするものである。 A carbon material for an electrode according to claim 13 of the present invention is characterized in that the polysaccharide-modified phenol resin carbonized material according to claim 10 is activated.
この発明によれば、多糖類変性フェノール樹脂炭化材料を賦活処理することによって比表面積や細孔容積を大きくすることができ、電極特性の優れた電極を形成することができるものである。 According to this invention, the specific surface area and the pore volume can be increased by activating the polysaccharide-modified phenolic resin carbonized material, and an electrode having excellent electrode characteristics can be formed.
本発明の請求項１４に係る電気二重層キャパシタ分極性電極は、請求項１０に記載の多糖類変性フェノール樹脂炭化材料を電極材料として形成されたことを特徴とするものである。 An electric double layer capacitor polarizable electrode according to claim 14 of the present invention is characterized in that the polysaccharide-modified phenol resin carbonized material according to claim 10 is used as an electrode material.
この発明によれば、多糖類変性フェノール樹脂炭化材料を用いて電極特性の優れた電気二重層キャパシタ分極性電極を形成することができるものである。 According to the present invention, an electric double layer capacitor polarizable electrode having excellent electrode characteristics can be formed using a polysaccharide-modified phenol resin carbonized material.
また本発明の請求項１５に係る電気二重層キャパシタ分極性電極は、請求項１３に記載の電極用炭素材料を電極材料として形成されたことを特徴とするものである。
An electric double layer capacitor polarizable electrode according to a fifteenth aspect of the present invention is characterized by being formed using the carbon material for an electrode according to the thirteenth aspect as an electrode material.
この発明によれば、賦活処理して比表面積や細孔容積を大きくした多糖類変性フェノール樹脂炭化材料を用いることによって、放・充電容量の高い電気二重層キャパシタ分極性電極を形成することができるものである。 According to the present invention, an electric double layer capacitor polarizable electrode having a high discharge / charge capacity can be formed by using a polysaccharide-modified phenol resin carbonized material whose specific surface area and pore volume are increased by activation treatment. Is.
本発明によれば、フェノール類と、アルデヒド類と、でんぷん糖、デキストリン、ザンサンガム、カードラン、プルラン、シクロアミロース、キチン、でんぷんから選ばれる多糖類とを、塩基性反応触媒の存在下で付加縮合反応させることによって、レゾール型の多糖類変性フェノール樹脂を得ることができるものであり、加熱することによって不溶不融状態にすることができ、レジンコーテッドサンド、炭化材料、導電性樹脂組成物、電極用炭素材料、二次電池用電極、電気二重層キャパシタ分極性電極など多様な用途に用いることができるものである。 According to the present invention, phenols, aldehydes, and polysaccharides selected from starch sugar, dextrin, xanthan gum, curdlan, pullulan, cycloamylose, chitin, and starch are subjected to addition condensation in the presence of a basic reaction catalyst. By reacting, a resol-type polysaccharide-modified phenol resin can be obtained, and by heating, it can be made insoluble and infusible, resin-coated sand, carbonized material, conductive resin composition, electrode It can be used for various applications such as carbon materials for use, electrodes for secondary batteries, and electric double layer capacitor polarizable electrodes.
以下、本発明を実施するための最良の形態を説明する。 Hereinafter, the best mode for carrying out the present invention will be described.
本発明の多糖類変性フェノール樹脂は、フェノール類と、アルデヒド類と、多糖類とを、塩基性反応触媒の存在下、付加縮合反応させることによって得ることができるものである。 The polysaccharide-modified phenolic resin of the present invention can be obtained by subjecting phenols, aldehydes, and polysaccharides to an addition condensation reaction in the presence of a basic reaction catalyst.
反応に使用するフェノール類としては、フェノールの他にフェノールの誘導体を用いることができる。フェノールの誘導体としては、例えばｍ−クレゾール、レゾルシノール、３，５−キシレノールなどの３官能性のもの、ビスフェノールＡ、ビスフェノールＳ、ジヒドロキシジフェニルメタンなどの４官能性のもの、ｏ−クレゾール、ｐ−クレゾール、ｐ−ｔｅｒ−ブチルフェノール、ｐ−フェニルフェノール、ｐ−クミルフェノール、ｐ−ノニルフェノール、２，４−又は２，６−キシレノールなどの２官能性のｏ−又はｐ−置換のフェノール類などを挙げることができ、さらに塩素又は臭素で置換されたハロゲン化フェノールなどを用いることもできる。フェノール類としてはこれらから１種を選択して用いる他、複数種のものを混合して用いることもできる。 As phenols used in the reaction, phenol derivatives can be used in addition to phenol. Examples of phenol derivatives include trifunctional compounds such as m-cresol, resorcinol and 3,5-xylenol, tetrafunctional compounds such as bisphenol A, bisphenol S, and dihydroxydiphenylmethane, o-cresol, p-cresol, List bifunctional o- or p-substituted phenols such as p-ter-butylphenol, p-phenylphenol, p-cumylphenol, p-nonylphenol, 2,4- or 2,6-xylenol In addition, halogenated phenols substituted with chlorine or bromine can also be used. As phenols, one type can be selected and used, or a plurality of types can be mixed and used.
また反応に使用するアルデヒド類としては、ホルムアルデヒドの水溶液の形態であるホルマリンが最適であるが、パラホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、トリオキサン、テトラオキサンのような形態のものを用いることもでき、その他アルデヒドの一部あるいは大部分をフルフラールやフルフリルアルコールに置き換えたものを用いることも可能である。 As the aldehydes used in the reaction, formalin, which is a formaldehyde aqueous solution, is optimal, but paraformaldehyde, acetaldehyde, benzaldehyde, trioxane, tetraoxane, and other aldehydes can be used. It is also possible to use those in which part or most of them are replaced with furfural or furfuryl alcohol.
また多糖類としては、でんぷん糖、デキストリン、ザンサンガム、カードラン、プルラン、シクロアミロース、キチン、でんぷんなどがあり、これらのうち一種を選択して、あるいは複数種を併用して、用いることができる。またでんぷんとしては、ばれいしょでんぷん、とうもろこしでんぷん、タピオカでんぷん、麦でんぷん、米でんぷん等や、これらの一部を変質させた、ヒドロキシプロピルでんぷん、カルボキシメチルでんぷん、カチオンでんぷん、酢酸でんぷん、オクテニルコハク酸でんぷん、リン酸でんぷん、グリセロールでんぷん、グラフト化でんぷん、あるいは焙焼した、白色デキストリン、黄色デキストリン、ブリティッシュガム、マルトデキストリン、可溶性でんぷん、未変性アルファ化でんぷん、変性アルファ化でんぷんなどを用いることもできる。 As also polysaccharides, starch sugar, dextrin, xanthan gum, curdlan, pullulan, cycloamylose, chitin, in include Npun, select one of these, or in combination of plural kinds, it is used it can. Starches include potato starch, corn starch, tapioca starch, wheat starch, rice starch, etc., and hydroxypropyl starch, carboxymethyl starch, cationic starch, acetate starch, octenyl succinate, Acid starch, glycerol starch, grafted starch, or roasted white dextrin, yellow dextrin, British gum, maltodextrin, soluble starch, unmodified pregelatinized starch, modified pregelatinized starch, and the like can also be used.
さらに付加縮合反応に使用する反応触媒としては、フェノール類とアルデヒド類を反応させ、ベンゼン核とベンゼン核の間に＝ＮＣＨ２−結合を生成するような塩基性物質、例えばヘキサメチレンテトラミン、アンモニア、メチルアミン、ジメチルアミン、エチレンジアミン、モノエタノールアミン等の第１級や第２級のアミン類などを用いることができる。また、ナトリウム、カリウム、リチウムなどアルカリ金属の酸化物、水酸化物、炭酸塩、あるいはカルシウム、マグネシウム、バリウムなどアルカリ土類金属の酸化物、水酸化物、炭酸塩、あるいは第３級アミン化合物などを挙げることもできる。これらの具体例を挙げると、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、水酸化カルシウム、水酸化マグネシウム、水酸化バリウム、炭酸カルシウム、酸化マグネシウム、酸化カルシウム、トリメチルアミン、トリエチルアミン、トリエタノールアミン、１，８−ジアザビシクロ〔５，４，０〕ウンデセン−７などがある。 Further, as a reaction catalyst used for the addition condensation reaction, a basic substance that reacts phenols and aldehydes to form a = NCH 2 -bond between the benzene nucleus and the benzene nucleus, such as hexamethylenetetramine, ammonia, Primary and secondary amines such as methylamine, dimethylamine, ethylenediamine, and monoethanolamine can be used. Also, alkali metal oxides such as sodium, potassium, lithium, hydroxides, carbonates, or alkaline earth metal oxides such as calcium, magnesium, barium, hydroxides, carbonates, tertiary amine compounds, etc. Can also be mentioned. Specific examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate, magnesium oxide, calcium oxide, trimethylamine, triethylamine, triethanol. Amines, 1,8-diazabicyclo [5,4,0] undecene-7, and the like.
上記各成分の配合量は、フェノール類１モルに対してアルデヒド類１．０〜３．０モルの範囲になるように、フェノール類に対するアルデヒド類の配合量を設定し、またフェノール類１００質量部に対して、多糖類１〜７０質量部の範囲が好ましい。また反応触媒の配合量は、反応触媒の種類によって大きく異なるが、フェノール類に対して０．０５〜１０質量％の範囲が好ましい。 The blending amount of each of the above components is such that the blending amount of the aldehydes with respect to the phenols is set in a range of 1.0 to 3.0 moles with respect to 1 mole of the phenols, and 100 parts by weight of the phenols. On the other hand, the range of 1-70 mass parts of polysaccharides is preferable. Moreover, although the compounding quantity of a reaction catalyst changes greatly with the kind of reaction catalyst, the range of 0.05-10 mass% with respect to phenols is preferable.
上記のようにして、レゾール型の多糖類変性フェノール樹脂を調製することができるものである。また、球状粒子の多糖類変性フェノール樹脂を調製する場合には、上記の付加縮合反応を、分散剤を添加した状態で行なうものである。分散剤は、一種の乳化剤としても作用するものであり、例えばアラビアゴム、ポリビニルアルコール、ニカワ、グアーゴム、タラガム、ガッテガム、カルボキシメチルセルロース、ヒドロキシエチルセルロース、可溶化でんぷん、寒天、アルギン酸ソーダなどを挙げることができ、これらのうちから一種単独で、あるいは複数種を併用して使用することができる。これらの中でも、アラビアゴム、タラガム、ポリビニルアルコールを好ましく用いることができる。分散剤の添加量は、分散剤が有する乳化効果によって大きく異なり、特に限定されるものではないが、フェノール類に対して０．１〜１０．０質量％の範囲が好ましく、特に０．５〜７．０質量％の範囲がより好ましい。 As described above, a resol-type polysaccharide-modified phenol resin can be prepared. In addition, when preparing a polysaccharide-modified phenol resin having spherical particles, the above addition condensation reaction is performed with a dispersant added. The dispersant acts as a kind of emulsifier, and examples thereof include gum arabic, polyvinyl alcohol, glue, guar gum, tara gum, gatter gum, carboxymethyl cellulose, hydroxyethyl cellulose, solubilized starch, agar, and sodium alginate. These can be used alone or in combination of two or more. Among these, gum arabic, tara gum, and polyvinyl alcohol can be preferably used. The amount of the dispersant added varies greatly depending on the emulsifying effect of the dispersant and is not particularly limited, but is preferably in the range of 0.1 to 10.0% by mass, particularly 0.5 to The range of 7.0% by mass is more preferable.
分散剤を添加して行なう付加縮合反応は、反応系を攪拌するに足る量の水中で、攪拌しつつ行なわれるものであり、反応の初期では反応液は透明であるが、付加縮合反応が進むと縮合反応物が系中の水分と分離し始め、これが分散剤の作用で凝集して球状になり、反応系中に析出する。そして所望する程度に反応を進めた後に、冷却し、攪拌を停止すると、反応系の水中で沈降し、水と分離する。このように沈降した材料は微小球形の含水粒状物となっているが、ろ過することによって容易に水から分離することができるものであり、これを乾燥することによって、球状の多糖類変性フェノール樹脂を得ることができるものである。 The addition condensation reaction performed by adding a dispersant is performed while stirring in an amount of water sufficient to stir the reaction system, and the reaction solution is transparent at the beginning of the reaction, but the addition condensation reaction proceeds. The condensation reaction product begins to separate from the water in the system, which aggregates into a spherical shape by the action of the dispersant and precipitates in the reaction system. Then, after the reaction has proceeded to the desired extent, cooling and stirring are stopped, it settles in the water of the reaction system and separates from the water. The material thus settled is a microspherical water-containing granular material, but it can be easily separated from water by filtration. By drying this, a spherical polysaccharide-modified phenolic resin is obtained. Can be obtained.
上記のようにして得られる多糖類変性フェノール樹脂において、多糖類の含有量は、多糖類変性による特性を必要且つ十分に得るために、１．０〜６０質量％の範囲が好ましい。例えば後述のようにレジンコーテッドサンドのバインダーとして多糖類変性フェノール樹脂を用いる場合、多糖類の含有量が１．０質量％未満では、崩壊性の良好な鋳型を成形することができなくなり、また多糖類の含有量が６０質量％を超えると、鋳型の曲げ強度が不十分となって、溶湯を鋳込む際に折れ等が生じて良好な鋳物を製造できなくなるおそれがある。あるいは、後述のように炭素材料として用いる場合、多糖類の含有量が１．０質量％未満では、比表面積の増加が少なく、また多糖類の含有量が６０質量％を超えると、比表面積は増加するが炭化物が脆くなって、良い電極を得ることが難しくなる。 In the polysaccharide-modified phenol resin obtained as described above, the content of the polysaccharide is preferably in the range of 1.0 to 60% by mass in order to obtain necessary and sufficient characteristics due to polysaccharide modification. For example, when a polysaccharide-modified phenol resin is used as the binder of the resin-coated sand as will be described later, when the content of the polysaccharide is less than 1.0% by mass, it becomes impossible to mold a mold having good disintegration. When the saccharide content exceeds 60% by mass, the bending strength of the mold becomes insufficient, and there is a possibility that bending or the like may occur when the molten metal is cast, making it impossible to manufacture a good casting. Alternatively, when used as a carbon material as described later, when the polysaccharide content is less than 1.0% by mass, the specific surface area increases little, and when the polysaccharide content exceeds 60% by mass, the specific surface area is Although increasing, the carbide becomes brittle and it becomes difficult to obtain a good electrode.
そしてこの多糖類変性フェノール樹脂は、フェノール類とアルデヒド類と多糖類を縮合させているために、樹脂の分子量が大きくなり、またレゾール型に調製されるために、熱硬化性を有するものである。このため、付加縮合反応を樹脂が熱硬化性を有する状態で停止することによって、未硬化で熱硬化性を有する多糖類変性フェノール樹脂を得ることができる。 The polysaccharide-modified phenolic resin has thermosetting properties because the molecular weight of the resin is increased because the phenols, aldehydes, and polysaccharides are condensed, and the resin is prepared into a resol type. . For this reason, the polysaccharide-modified phenol resin which is uncured and has thermosetting property can be obtained by stopping the addition condensation reaction in a state where the resin has thermosetting property.
この未硬化で熱硬化性の多糖類変性フェノール樹脂は、加熱することによって溶融・硬化するので、成形材料として用いることができるものである。成形は、多糖類変性フェノール樹脂を金型に射出する射出成形や、金型に充填して加熱・加圧する圧縮成形など任意の成形法で行なうことができる。このときの加熱は、金型の温度を１３０〜２５０℃の範囲に設定して行なうのが好ましく、加圧は、１０〜２００ＭＰａの範囲の面圧で行なうのが好ましい。 This uncured and thermosetting polysaccharide-modified phenolic resin can be used as a molding material because it is melted and cured by heating. The molding can be performed by any molding method such as injection molding in which a polysaccharide-modified phenol resin is injected into a mold, or compression molding in which the mold is filled and heated and pressurized. The heating at this time is preferably performed with the mold temperature set in the range of 130 to 250 ° C., and the pressing is preferably performed at a surface pressure in the range of 10 to 200 MPa.
またこの未硬化で熱硬化性の多糖類変性フェノール樹脂を用いて、レジンコーテッドサンドを得ることができる。レジンコーテッドサンドの製造は、例えば、けい砂など鋳型用の耐火骨材を１５０℃程度に加熱し、この加熱した耐火骨材に未硬化で熱硬化性の多糖類変性フェノール樹脂０．８〜３．０質量％程度添加して、混練した後に、冷却することによって行なうことができ、さらさらとしたレジンコーテッドサンドを得ることができるものである。 Further, a resin-coated sand can be obtained using this uncured and thermosetting polysaccharide-modified phenol resin. The resin-coated sand is produced, for example, by heating a refractory aggregate for a mold such as silica sand to about 150 ° C., and the heated refractory aggregate is uncured and thermosetting polysaccharide-modified phenolic resin 0.8-3. About 0.0% by mass can be added, kneaded and then cooled, and a smooth resin-coated sand can be obtained.
このレジンコーテッドサンドは、耐火骨材にコーティングされる多糖類変性フェノール樹脂がバインダーとなって、シェルモールドなどの鋳型を成形することができるものである。ここで、例えば自動車産業では、軽量化して燃費の低減を図るため、鋳鉄に比較して軽いアルミニウムやマグネシウム合金を使用して鋳造を行なうことが多いが、これらの金属の溶融温度は６００〜７００℃と低い。そして、従来からレジンコーテッドサンドに汎用されているフェノール樹脂は耐熱性が高いので、このようなフェノール樹脂をバインダーとするレジンコーテッドサンドで作製した鋳型は、溶融金属の温度でフェノール樹脂バインダーを十分に熱分解することができず、鋳造後の鋳型の崩壊性に問題がある。一方、本発明の多糖類変性フェノール樹脂は多糖類変性によって熱分解温度を低くすることができるものであり、この多糖類変性フェノール樹脂をレジンコーテッドサンドのバインダーとして用いることによって、崩壊性の良好な鋳型を成形することができるものである。 This resin-coated sand can form a mold such as a shell mold using a polysaccharide-modified phenol resin coated on a refractory aggregate as a binder. Here, for example, in the automobile industry, in order to reduce weight and reduce fuel consumption, casting is often performed using lighter aluminum or magnesium alloy than cast iron, but the melting temperature of these metals is 600 to 700. As low as ℃. Since phenolic resins that have been widely used for resin-coated sands have high heat resistance, molds made with resin-coated sands that use such phenolic resins as binders are sufficient to use phenolic resin binders at the temperature of the molten metal. It cannot be pyrolyzed, and there is a problem in the mold disintegration after casting. On the other hand, the polysaccharide-modified phenolic resin of the present invention can lower the thermal decomposition temperature by polysaccharide modification. By using this polysaccharide-modified phenolic resin as a binder for resin-coated sand, the disintegration is good. A mold can be formed.
また、上記のようにして多糖類変性フェノール樹脂を調製するにあたって、付加縮合反応を、生成される多糖類変性フェノール樹脂が不溶不融性になるまで持続した後に、停止させることによって、完全硬化状態の多糖類変性フェノール樹脂を得ることができるものである。尚、完全硬化状態の多糖類変性フェノール樹脂を得るにあたっては、このように生成される多糖類変性フェノール樹脂が不溶不融性になるまで付加縮合反応を持続するようにする他に、上記のように未硬化の多糖類変性フェノール樹脂を調製した後に、これを加熱処理して多糖類変性フェノール樹脂を完全硬化させるようにしてもよい。 Further, in preparing the polysaccharide-modified phenol resin as described above, the addition condensation reaction is continued until the produced polysaccharide-modified phenol resin becomes insoluble and infusible, and then is completely cured. The polysaccharide-modified phenolic resin can be obtained. In obtaining a fully cured polysaccharide-modified phenol resin, the addition condensation reaction is continued until the polysaccharide-modified phenol resin thus produced becomes insoluble and infusible. After preparing an uncured polysaccharide-modified phenolic resin, it may be heat-treated to completely cure the polysaccharide-modified phenolic resin.
この完全硬化して不溶不融状態になった多糖類変性フェノール樹脂は、例えばフィラーなどとして使用することができる。特に、分散剤の存在下で付加縮合反応を行なって球状に調製される多糖類変性フェノール樹脂は、流動性に優れたフィラーとして使用することができるものである。 The polysaccharide-modified phenolic resin that has been completely cured to be insoluble and infusible can be used, for example, as a filler. In particular, a polysaccharide-modified phenol resin prepared in a spherical shape by performing an addition condensation reaction in the presence of a dispersant can be used as a filler excellent in fluidity.
またこの完全硬化した状態の多糖類変性フェノール樹脂を、非酸化性雰囲気で熱処理して、多糖類変性フェノール樹脂を炭化させることによって、多糖類変性フェノール樹脂炭化材料を得ることができるものである。非酸化性雰囲気は、多糖類変性フェノール樹脂が酸化されないものであればよく、例えば不活性ガス雰囲気としてアルゴン、ヘリウム、窒素ガスなどの雰囲気に設定することができる。熱処理の条件は、多糖類変性フェノール樹脂を焼成して炭化するために、４００〜３０００℃、１〜１００時間程度に設定するのが好ましい。 Further, the polysaccharide-modified phenol resin carbonized material can be obtained by heat-treating the polysaccharide-modified phenol resin in a completely cured state in a non-oxidizing atmosphere to carbonize the polysaccharide-modified phenol resin. The non-oxidizing atmosphere is not particularly limited as long as the polysaccharide-modified phenolic resin is not oxidized. For example, an inert gas atmosphere such as argon, helium, or nitrogen gas can be set. The heat treatment conditions are preferably set to 400 to 3000 ° C. and about 1 to 100 hours in order to calcine and carbonize the polysaccharide-modified phenol resin.
この多糖類変性フェノール樹脂炭化材料は導電性フィラーとして用いることができ、多糖類変性フェノール樹脂炭化材料を樹脂に配合することによって、導電性樹脂組成物を得ることができるものである。特に、分散剤の存在下で付加縮合反応を行なって球状に調製される多糖類変性フェノール樹脂を炭化させた多糖類変性フェノール樹脂炭化材料は、流動性に優れた導電性フィラーとして使用することができるものである。 This polysaccharide-modified phenolic resin carbonized material can be used as a conductive filler, and a conductive resin composition can be obtained by blending a polysaccharide-modified phenolic resin carbonized material with a resin. In particular, a polysaccharide-modified phenol resin carbonized material obtained by carbonizing a polysaccharide-modified phenol resin prepared in a spherical shape by performing an addition condensation reaction in the presence of a dispersant can be used as a conductive filler having excellent fluidity. It can be done.
導電性樹脂組成物の樹脂としては、ポリフェニレンサルファイド樹脂、ポリフェニレンエーテル樹脂、液晶ポリマー、ポリスチレン樹脂、ＡＢＳ樹脂、ポリアセタール樹脂、ポリカーボネート樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリ塩化ビニル樹脂、ポリアミド樹脂、ポリスチレン樹脂などの熱可塑性樹脂や、フェノール樹脂、不飽和ポリエステル樹脂、エポキシ樹脂などの熱硬化性樹脂を用いることができる。導電性フィラーとして配合する多糖類変性フェノール樹脂炭化材料の配合量は任意に設定することができるが、質量比で樹脂１に対して、多糖類変性フェノール樹脂炭化材料を０．０１〜１．５程度の範囲に設定するのが好ましい。 Examples of the resin of the conductive resin composition include polyphenylene sulfide resin, polyphenylene ether resin, liquid crystal polymer, polystyrene resin, ABS resin, polyacetal resin, polycarbonate resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyamide resin, polystyrene resin, etc. Thermosetting resins such as phenolic resins, unsaturated polyester resins, and epoxy resins can be used. Although the compounding quantity of the polysaccharide modification phenol resin carbonization material mix | blended as an electroconductive filler can be set arbitrarily, 0.01-1.5 is a polysaccharide modification phenol resin carbonization material with respect to the resin 1 by mass ratio. It is preferable to set a range of about.
このように調製される導電性樹脂組成物を射出成形や圧縮成形などの任意の方法で成形することによって、導電性の高い電気・電子機器の部品などを製造することができるものである。 By molding the conductive resin composition thus prepared by an arbitrary method such as injection molding or compression molding, it is possible to manufacture parts of electric / electronic devices having high conductivity.
また、上記のように多糖類変性フェノール樹脂を非酸化性雰囲気で熱処理する際に、多糖類変性フェノール樹脂は熱に曝されることによって熱分解を起こし、低分子量物質となった分解生成物が揮散し、その抜け跡が空隙となるので、多糖類変性フェノール樹脂炭化材料の粒子には多数の細孔が形成されるものである。特に多糖類変性フェノール樹脂の炭化物収率は一般のフェノール樹脂よりも小さく、その分、熱分解ガスが抜け易いものであり、細孔容積が大きく、また比表面積が大きくなる。このため、多糖類変性フェノール樹脂炭化材料の粒子には活性炭と同様な効果を発揮させることもできるものである。 In addition, when the polysaccharide-modified phenolic resin is heat-treated in a non-oxidizing atmosphere as described above, the polysaccharide-modified phenolic resin undergoes thermal decomposition when exposed to heat, and the decomposition product that has become a low molecular weight substance is present. Volatilization occurs and the traces become voids, so that a large number of pores are formed in the particles of the polysaccharide-modified phenol resin carbonized material. In particular, the yield of the carbide of the polysaccharide-modified phenol resin is smaller than that of a general phenol resin, and the pyrolysis gas easily escapes accordingly, and the pore volume is large and the specific surface area is large. For this reason, the polysaccharide modified phenolic resin carbonized material particles can also exhibit the same effect as activated carbon.
従って、この多糖類変性フェノール樹脂炭化材料を、リチウムイオン二次電池の負極など二次電池の電極を形成する炭素材料として使用することができるものである。多糖類変性フェノール樹脂炭化材料を電極用炭素材料として用いて、リチウムイオン二次電池の負極などの電極を作製するにあたっては、例えば、多糖類変性フェノール樹脂炭化材料をバインダーと共に溶剤等に分散してスラリー状にし、銅箔等の金属箔にこのスラリーを塗布して乾燥し、プレス成形等することによって行なうことができるものである。 Therefore, this polysaccharide-modified phenol resin carbonized material can be used as a carbon material for forming an electrode of a secondary battery such as a negative electrode of a lithium ion secondary battery. In producing an electrode such as a negative electrode of a lithium ion secondary battery using a polysaccharide-modified phenol resin carbonized material as an electrode carbon material, for example, a polysaccharide-modified phenol resin carbonized material is dispersed in a solvent together with a binder. The slurry can be formed into a slurry, applied to a metal foil such as a copper foil, dried, press-molded, and the like.
さらに、この電極を分極性電極として用い、電解液の界面で形成される電気二重層を形成する電気二重層キャパシタを形成することができるものである。 Furthermore, this electrode can be used as a polarizable electrode to form an electric double layer capacitor that forms an electric double layer formed at the interface of the electrolytic solution.
このように、本発明の多糖類変性フェノール樹脂炭化材料を用いて二次電池用電極や、電気二重層キャパシタ分極性電極を作製することによって、充・放電容量が高い二次電池や電気二重層キャパシタを得ることができるものである。 Thus, by producing the electrode for a secondary battery or the electric double layer capacitor polarizable electrode using the polysaccharide-modified phenol resin carbonized material of the present invention, the secondary battery or the electric double layer having a high charge / discharge capacity. A capacitor can be obtained.
ここで、電気二重層キャパシタの分極性電極は、多くのイオンを吸着できるように比表面積の大きい活性炭が電極材料として用いられており、本発明に係る多糖類変性フェノール樹脂炭化材料も既述のように、熱処理して多糖類変性フェノール樹脂を炭化させることによって活性炭と同じ効果を有する細孔を具備し、大きな比表面積や細孔容積を有している。 Here, as the polarizable electrode of the electric double layer capacitor, activated carbon having a large specific surface area is used as an electrode material so that many ions can be adsorbed, and the polysaccharide-modified phenolic resin carbonized material according to the present invention is also described above. Thus, it has the pore which has the same effect as activated carbon by carbonizing the polysaccharide modified phenolic resin by heat treatment, and has a large specific surface area and pore volume.
しかしこのように多糖類変性フェノール樹脂の炭化で生成される細孔では、比表面積や細孔容積は十分に大きいものではなく、必ずしも満足できるものではない。そこで本発明では多糖類変性フェノール樹脂炭化材料を、水蒸気や二酸化炭素等による気相賦活法、溶融水酸化カリウム等による薬液賦活法などにより賦活処理して、多糖類変性フェノール樹脂炭化材料の単位質量当りの比表面積及び細孔容積をさらに大きくし、物理的化学的吸着性能を向上させた電極用炭素材料を製造するようにしている。そしてこの電極用炭素材料で電気二重層キャパシタ分極性電極を作製することによって、充・放電容量が高い電気二重層キャパシタを得ることができるものである。 However, the pores generated by the carbonization of the polysaccharide-modified phenol resin are not sufficiently large in specific surface area and pore volume, and are not always satisfactory. Therefore, in the present invention, the polysaccharide-modified phenolic resin carbonized material is activated by a gas phase activation method using water vapor or carbon dioxide, a chemical solution activation method using molten potassium hydroxide, etc., and the unit mass of the polysaccharide-modified phenolic resin carbonized material. A carbon material for an electrode having an increased physical surface area and pore volume and improved physical and chemical adsorption performance is manufactured. An electric double layer capacitor having a high charge / discharge capacity can be obtained by producing an electric double layer capacitor polarizable electrode using the carbon material for an electrode.
次に、本発明を実施例によって具体的に説明する。 Next, the present invention will be specifically described with reference to examples.
（実施例１：未硬化のでんぷん変性フェノール樹脂の製造）
反応容器に、フェノールを４００質量部、でんぷんとして日澱化學（株）製架橋澱粉「ＰＢ−７０００」を１００質量部、３７質量％濃度のホルマリンを４０５質量部、水を５００質量部、塩基性反応触媒としてヘキサメチレンテトラミンを５０質量部仕込み、これを攪拌しながら約６０分を要して内温７０℃になるまで昇温し、内温７０℃で６時間、付加縮合反応をさせた。
(Example 1: Production of uncured starch-modified phenol resin)
In a reaction vessel, phenol is 400 parts by weight, starch is 100 parts by weight of cross-linked starch “PB-7000” manufactured by Nissho Kagaku Co., Ltd., 405 parts by weight of 37% by weight formalin, 500 parts by weight of water, basic As a reaction catalyst, 50 parts by mass of hexamethylenetetramine was charged, and the mixture was stirred and heated for about 60 minutes until the internal temperature reached 70 ° C., and an addition condensation reaction was carried out at the internal temperature of 70 ° C. for 6 hours.
次に、０．０１ＭＰａ（１００トール）で減圧脱液を開始し、９０℃まで行なった後、反応生成物をステンレス製のバットに払い出して冷却した。 Next, vacuum degassing was started at 0.01 MPa (100 Torr), and after 90 ° C., the reaction product was discharged into a stainless steel vat and cooled.
得られたレゾール型のでんぷん変性フェノール樹脂の軟化点とゲル化時間をＪＩＳ Ｋ ６９１０に準拠して測定したところ、軟化点は７６．８℃、１５０℃におけるゲル化時間は９８秒であった。また固定炭素量は４７．６質量％であった。 When the softening point and gelation time of the obtained resol-type starch-modified phenol resin were measured according to JIS K 6910, the softening point was 76.8 ° C. and the gelation time at 150 ° C. was 98 seconds. The amount of fixed carbon was 47.6% by mass.
（実施例２：未硬化の球状のでんぷん変性フェノール樹脂の製造）
上記の実施例１において、分散剤として（株）クラレ製ポリビニルアルコール「ＰＶＡ−２２４」を１０質量部加えるようにした他は、実施例１と同様にして付加縮合反応をさせた。
(Example 2: Production of uncured spherical starch-modified phenol resin)
In Example 1 above, an addition condensation reaction was performed in the same manner as in Example 1 except that 10 parts by mass of Kuraray Co., Ltd. polyvinyl alcohol “PVA-224” was added as a dispersant.
そして減圧脱液をせずに冷却し、ヌッチェで濾別して、球状の生成物を取り出し、バットに載せた紙の上で一週間風乾させることによって、球状のでんぷん変性フェノール樹脂を得た。 And it cooled without carrying out pressure reduction liquid removal, it filtered by Nutsche, the spherical product was taken out, and the spherical starch modified phenol resin was obtained by air-drying on the paper mounted on the vat for one week.
得られた球状のでんぷん変性フェノール樹脂の軟化点は７５．２℃、１５０℃におけるゲル化時間は１１３秒、固定炭素量は４３．８質量％であった。また平均粒径は３３μｍであった。 The resulting spherical starch-modified phenol resin had a softening point of 75.2 ° C., a gel time at 150 ° C. of 113 seconds, and a fixed carbon content of 43.8% by mass. The average particle size was 33 μm.
（実施例３：硬化したでんぷん変性フェノール樹脂の製造）
上記の実施例１で得たでんぷん変性フェノール樹脂をステンレス製のバットに広げ、予め１００℃に庫内温度を設定した乾燥器中に入れて、１０時間養生し、さらに１２０℃にして５時間養生することによって、でんぷん変性フェノール樹脂を硬化させた。
(Example 3: Production of cured starch-modified phenolic resin)
The starch-modified phenolic resin obtained in Example 1 above is spread on a stainless steel vat, placed in a drier previously set at 100 ° C., and cured for 10 hours, and further cured at 120 ° C. for 5 hours. By doing so, the starch-modified phenolic resin was cured.
次に冷却した後、０．５ｍｍの網を備えたハンマークラッシャーで粉砕して、不溶不融状態に硬化したでんぷん変性フェノール樹脂を得た。 Next, after cooling, it was pulverized with a hammer crusher equipped with a 0.5 mm net to obtain a starch-modified phenol resin cured in an insoluble and infusible state.
（実施例４：硬化した球状のでんぷん変性フェノール樹脂の製造）
上記の実施例２において、付加縮合反応を、攪拌しながら６０分を要して沸騰還流状態にし、この温度で４時間、行なうようにした。その他は、上記の実施例２と同様にして不溶不融状態に硬化した球状のでんぷん変性フェノール樹脂を得た。
(Example 4: Production of cured spherical starch-modified phenol resin)
In Example 2 described above, the addition condensation reaction was carried out at the temperature for 4 hours while stirring and was brought to the boiling reflux state for 60 minutes. In other respects, a spherical starch-modified phenol resin cured in an insoluble and infusible state was obtained in the same manner as in Example 2 above.
（比較例１：未硬化のフェノール樹脂の製造）
反応容器にフェノールを６６０質量部、３７質量％濃度のホルマリンを７１２質量部、ヘキサメチレンテトラミンを７５質量部、水を１２０質量部仕込み、約６０分を要して７０℃に昇温し、このまま４時間反応を行なった。
(Comparative Example 1: Production of uncured phenol resin)
A reaction vessel was charged with 660 parts by weight of phenol, 712 parts by weight of formalin having a concentration of 37% by weight, 75 parts by weight of hexamethylenetetramine, and 120 parts by weight of water, and the temperature was raised to 70 ° C. in about 60 minutes. The reaction was performed for 4 hours.
次に、０．０１ＭＰａ（１００トール）で減圧脱液を開始し、９０℃まで行なった後、反応生成物をステンレス製のバットに払い出して冷却した。 Next, vacuum degassing was started at 0.01 MPa (100 Torr), and after 90 ° C., the reaction product was discharged into a stainless steel vat and cooled.
得られたレゾール型のフェノール樹脂の軟化点は７７．３℃、１５０℃におけるゲル化時間は９３秒であった。また固定炭素量は５１．２質量％であった。 The resulting resol-type phenol resin had a softening point of 77.3 ° C. and a gel time at 150 ° C. of 93 seconds. The amount of fixed carbon was 51.2% by mass.
（比較例２：未硬化の球状のフェノール樹脂の製造）
攪拌装置を備えた反応容器にフェノールを４５０質量部、３７質量％濃度のホルマリンを４６０質量部、ヘキサメチレンテトラミンを５０質量部、分散剤としてアラビアゴムを４．５質量部、水を１２０質量部仕込み、これを攪拌しながら約６０分を要して８０℃に昇温し、このまま３時間、付加縮合反応を行なった。
(Comparative Example 2: Production of uncured spherical phenol resin)
In a reaction vessel equipped with a stirrer, 450 parts by mass of phenol, 460 parts by mass of 37% by weight formalin, 50 parts by mass of hexamethylenetetramine, 4.5 parts by mass of gum arabic as a dispersant, and 120 parts by mass of water The mixture was charged and stirred for about 60 minutes, and the temperature was raised to 80 ° C., and the addition condensation reaction was carried out for 3 hours as it was.
次に反応容器の内温が３０℃になるまで冷却した後、ヌッチェで濾別して、球状の生成物を取り出し、バットに載せた紙の上で一週間風乾させることによって、球状のフェノール樹脂を得た。 Next, after cooling until the internal temperature of the reaction vessel reaches 30 ° C., the product is filtered with Nutsche, and the spherical product is taken out and air-dried on paper placed on a bat for one week to obtain a spherical phenol resin. It was.
得られた球状のフェノール樹脂の軟化点は７６．５℃、１５０℃におけるゲル化時間は９８秒、固定炭素量は５２．３質量％であった。また平均粒径は４３μｍであった。 The obtained spherical phenol resin had a softening point of 76.5 ° C., a gelation time at 150 ° C. of 98 seconds, and a fixed carbon content of 52.3 mass%. The average particle size was 43 μm.
（比較例３：硬化したフェノール樹脂の製造）
上記の比較例１で得たフェノール樹脂を、上記の実施例３と同様にして加熱養生すると共に粉砕することによって、不溶不融状態に硬化したフェノール樹脂を得た。
(Comparative Example 3: Production of cured phenolic resin)
The phenol resin obtained in the above Comparative Example 1 was heated and cured in the same manner as in Example 3 and pulverized to obtain a phenol resin cured in an insoluble and infusible state.
（比較例４：硬化した球状のフェノール樹脂の製造）
上記の比較例２において、付加縮合反応を、攪拌しながら６０分を要して沸騰還流状態にし、この温度で４時間行なうことによって、不溶不融状態に硬化した球状のフェノール樹脂を得た。得られた球状のフェノール樹脂の平均粒径は４８μｍであった。
(Comparative Example 4: Production of cured spherical phenol resin)
In the above Comparative Example 2, the addition condensation reaction was brought to a boiling reflux state with stirring for 60 minutes and carried out at this temperature for 4 hours to obtain a spherical phenol resin cured in an insoluble and infusible state. The average particle diameter of the obtained spherical phenol resin was 48 μm.
（実施例５〜６）
１４５℃に加熱したフラタリーけい砂３０ｋｇをワールミキサーにいれ、これに実施例１あるいは実施例２で得た未硬化のでんぷん変性フェノール樹脂４５０ｇを加え、３０秒間混練した後、さらに水４５０ｇを添加し、砂粒が崩壊するまで混練した。次いで、ステアリン酸カルシウム３０ｇを添加して３０秒間混練した後、これをワールミキサーから払い出し、エアレーションを行なって冷却することによって、けい砂の表面にでんぷん変性フェノール樹脂を被覆したレジンコーテッドサンドを得た。
(Examples 5-6)
Add 30 kg of flattered silica sand heated to 145 ° C. to a whirl mixer, add 450 g of uncured starch-modified phenolic resin obtained in Example 1 or Example 2, knead for 30 seconds, and then add 450 g of water. The mixture was kneaded until the sand grains collapsed. Next, after adding 30 g of calcium stearate and kneading for 30 seconds, this was discharged from a whirl mixer, aerated and cooled to obtain a resin-coated sand in which the surface of silica sand was coated with a starch-modified phenol resin.
このレジンコーテッドサンドは、けい砂に対するでんぷん変性フェノール樹脂の被覆量が１．５質量％であり、さらさらとして流動性が良好なものであった。 This resin-coated sand had a starch-modified phenolic resin coating amount of 1.5% by mass with respect to silica sand, and was excellent in fluidity.
（比較例５〜６）
比較例１あるいは比較例２で得た未硬化のフェノール樹脂を用いるようにした他は、実施例５〜６と同様にして、けい砂の表面にフェノール樹脂を被覆したレジンコーテッドサンドを得た。このレジンコーテッドサンドは、けい砂に対するフェノール樹脂の被覆量が１．５質量％であった。
(Comparative Examples 5-6)
Resin-coated sand in which the surface of silica sand was coated with phenol resin was obtained in the same manner as in Examples 5-6 except that the uncured phenol resin obtained in Comparative Example 1 or Comparative Example 2 was used. This resin-coated sand had a phenol resin coating amount of 1.5% by mass with respect to silica sand.
上記のようにして実施例５〜６及び比較例５〜６で得たレジンコーテッドサンドについて、融着点、かさ比重、流下時間、安息角を測定した。融着点の測定はＪＡＣＴ試験法Ｃ−１に準拠して行ない、かさ比重の測定は共和理化工業株式会社製のかさ比重測定器Ａ型を用いて、ＪＩＳ Ｋ ６７２１に準拠して行なった。流下時間の測定はＪＩＳ Ｋ ５４０２に規定されるフォードカップを用い、ＪＡＣＴ試験法Ｓ−５に準拠して行なった。安息角は、筒井理化学器械株式会社製「ＡＯＤ粉体特性測定器」を用いて測定した。 About the resin coated sand obtained in Examples 5-6 and Comparative Examples 5-6 as described above, the fusion point, bulk specific gravity, flow-down time, and angle of repose were measured. The fusion point was measured according to JACT test method C-1, and the bulk specific gravity was measured according to JIS K 6721 using a bulk specific gravity measuring instrument A type manufactured by Kyowa Rika Kogyo Co., Ltd. The flow-down time was measured according to JACT test method S-5 using a Ford cup defined in JIS K5402. The angle of repose was measured using an “AOD powder property measuring instrument” manufactured by Tsutsui Riken Kikai Co., Ltd.
また、実施例５〜６及び比較例５〜６で得たレジンコーテッドサンドを用い、ＪＩＳ Ｋ ６９１０の曲げ強さ試験法に従って試験片を作製し、曲げ強さを測定した。そしてこの未焼成時の曲げ強さと、熱に暴露して焼成した後の曲げ強さとを比較し、（焼成後の曲げ強さ／焼成前の曲げ強さ）を強度の保持率として、鋳型の崩壊性を評価した。焼成は、上記のように曲げ強さ測定用に作製した試験片をアルミニウム箔に包み、これを３５０℃あるいは４００℃に設定した電気炉に３０秒あるいは６０秒入れて熱処理することによって行ない、冷却後に曲げ強さを測定した。 Moreover, using the resin-coated sand obtained in Examples 5 to 6 and Comparative Examples 5 to 6, test pieces were prepared according to the bending strength test method of JIS K 6910, and the bending strength was measured. Then, this unfired bending strength is compared with the bending strength after firing by exposure to heat, and (the bending strength after firing / the bending strength before firing) as the strength retention, Disintegration was evaluated. Firing is performed by wrapping the test piece prepared for measuring the bending strength as described above in aluminum foil and heat-treating it in an electric furnace set at 350 ° C. or 400 ° C. for 30 seconds or 60 seconds. Later, the bending strength was measured.
表１にみられるように、実施例５，６のものは、焼成後の保持率が低く、鋳型の崩壊性が良好であることが確認される。 As seen in Table 1, it is confirmed that the examples 5 and 6 have low retention after firing and good mold disintegration.
（実施例７：でんぷん変性フェノール樹脂炭化材料の製造）
実施例３で得た硬化したでんぷん変性フェノール樹脂を、窒素雰囲気下、１００℃／ｈの昇温速度で８００℃まで昇温し、８００℃で３時間保持する条件で熱処理することによって焼成し、でんぷん変性フェノール樹脂炭化材料の粒子を得た。このでんぷん変性フェノール樹脂炭化材料の収率は４５．８質量％であった。
(Example 7: Production of starch-modified phenolic resin carbonized material)
The cured starch-modified phenolic resin obtained in Example 3 was baked by heat treatment under a nitrogen atmosphere at a heating rate of 100 ° C./h up to 800 ° C. and maintained at 800 ° C. for 3 hours, Starch-modified phenolic resin carbonized particles were obtained. The yield of the starch-modified phenolic resin carbonized material was 45.8% by mass.
（実施例８：でんぷん変性フェノール樹脂炭化材料の製造）
実施例４で得た硬化したでんぷん変性フェノール樹脂を用いるようにした他は、実施例７と同様にして焼成し、でんぷん変性フェノール樹脂炭化材料の粒子を得た。このでんぷん変性フェノール樹脂炭化材料の収率は４３．３質量％であった。
(Example 8: Production of starch-modified phenolic resin carbonized material)
Baking was performed in the same manner as in Example 7 except that the cured starch-modified phenol resin obtained in Example 4 was used, and particles of the starch-modified phenol resin carbonized material were obtained. The yield of the starch-modified phenolic resin carbonized material was 43.3% by mass.
（比較例７：フェノール樹脂炭化材料の製造）
比較例３で得た硬化したフェノール樹脂を用いるようにした他は、実施例７と同様にして焼成し、フェノール樹脂炭化材料の粒子を得た。このフェノール樹脂炭化材料の収率は５１．３質量％であった。
(Comparative Example 7: Production of phenolic resin carbonized material)
Baking was performed in the same manner as in Example 7 except that the cured phenol resin obtained in Comparative Example 3 was used, thereby obtaining particles of a phenol resin carbonized material. The yield of this phenol resin carbonized material was 51.3% by mass.
（比較例８：フェノール樹脂炭化材料の製造）
比較例４で得た硬化したフェノール樹脂を用いるようにした他は、実施例７と同様にして焼成し、フェノール樹脂炭化材料の粒子を得た。このフェノール樹脂炭化材料の収率は５２．１質量％であった。
(Comparative Example 8: Production of phenol resin carbonized material)
Baking was performed in the same manner as in Example 7 except that the cured phenol resin obtained in Comparative Example 4 was used, thereby obtaining particles of a phenol resin carbonized material. The yield of this phenol resin carbonized material was 52.1% by mass.
（実施例９〜１０、比較例９〜１０）
上記の実施例７〜８及び比較例７〜８で得た炭化材料を４０質量部、ポリフェニレンエーテル樹脂（三菱エンジニアリングプラスチック（株）製「ユピエースＡＨ８」）を６０質量部とり、これをドライブレンドした後、ラボテストミルを用いて３２０℃で均一に溶融混練した。そしてこれを冷却して固化させた後、粉砕することによって、導電性樹脂組成物を得た。
(Examples 9 to 10, Comparative Examples 9 to 10)
40 parts by mass of the carbonized material obtained in Examples 7 to 8 and Comparative Examples 7 to 8 above and 60 parts by mass of polyphenylene ether resin (“Iupiace AH8” manufactured by Mitsubishi Engineering Plastics) were dry blended. Then, it melt-kneaded uniformly at 320 degreeC using the laboratory test mill. And after cooling and solidifying this, the conductive resin composition was obtained by grind | pulverizing.
次に、この導電性樹脂組成物を射出成形することによって、縦・横が１００ｍｍ、厚さ２ｍｍの樹脂成形体を作製した。この樹脂成形体について、抵抗率をＪＩＳ Ｋ ７１９４に準拠して測定し、その結果を表２に示す。 Next, this conductive resin composition was injection-molded to produce a resin molded body having a length and width of 100 mm and a thickness of 2 mm. About this resin molding, a resistivity was measured based on JISK7194, and the result is shown in Table 2.
表２にみられるように、各実施例のものは抵抗率が小さく、導電性に優れることが確認される。 As seen in Table 2, it is confirmed that each example has a low resistivity and excellent conductivity.
（実施例１１〜１２及び比較例１１〜１２）
実施例７〜８及び比較例７〜８で得た炭化材料３ｇに、ポリビニリデンフルオライドをＮ−メチルピロリドンに１０質量％溶解させて調製したバインダー３ｇを加え、これを混合してスラリー状にした。そしてこのスラリーを厚さ２０μｍ、直径１２ｍｍの円形の銅箔に塗布し、１３０℃で１０時間真空乾燥した後、減圧下でプレス成形して電極を作製した。
(Examples 11-12 and Comparative Examples 11-12)
3 g of a binder prepared by dissolving 10% by mass of polyvinylidene fluoride in N-methylpyrrolidone was added to 3 g of the carbonized material obtained in Examples 7 to 8 and Comparative Examples 7 to 8, and this was mixed to form a slurry. did. Then, this slurry was applied to a circular copper foil having a thickness of 20 μm and a diameter of 12 mm, vacuum-dried at 130 ° C. for 10 hours, and then press-molded under reduced pressure to produce an electrode.
上記の実施例１１〜１２及び比較例１１〜１２で得た電極について、充・放電容量を測定した。充・放電容量測定には２電極セルを用いた。対極に金属リチウム、作用極に炭素材料を使用し、セパレータにはポリプロピレン製多孔質膜を用いた。電解液は１モル濃度の過塩素酸リチウムのエチレンカーボネート／ジエチレンカーボネート溶液（５０／５０質量％）を用いた。そして充・放電は正極、負極間に２５ｍＡ／ｇの定電流を流して行ない、両極間の電位差の経時変化を測定することにより放電時間と充電時間を求めた。放電容量は、電流密度が一定であるため電流密度に放電時間又は充電時間を積算することにより求めた。またこの放電を１サイクルとして、２０サイクル充・放電を繰り返した後についても、同様に放電容量を求めた。結果を表３に示す。 The charge / discharge capacity of the electrodes obtained in Examples 11 to 12 and Comparative Examples 11 to 12 was measured. A two-electrode cell was used for charge / discharge capacity measurement. Metal lithium was used for the counter electrode, a carbon material was used for the working electrode, and a polypropylene porous membrane was used for the separator. As the electrolytic solution, an ethylene carbonate / diethylene carbonate solution (50/50% by mass) of 1 molar lithium perchlorate was used. Charging / discharging was carried out by flowing a constant current of 25 mA / g between the positive electrode and the negative electrode, and the change over time in the potential difference between the two electrodes was measured to determine the discharge time and the charge time. The discharge capacity was determined by integrating the discharge time or the charge time with the current density because the current density was constant. In addition, the discharge capacity was determined in the same manner even after 20 cycles of charging and discharging were repeated with this discharge as one cycle. The results are shown in Table 3.
表３にみられるように、各実施例のものは、放電容量が大きく、また充・放電を繰り返しても放電容量の低下が少なく、電池寿命を延ばすことができることが確認される。 As can be seen from Table 3, it is confirmed that each of the examples has a large discharge capacity, and even when charging and discharging are repeated, the decrease in the discharge capacity is small and the battery life can be extended.
（実施例１３〜１４及び比較例１３〜１４）
実施例７〜８及び比較例７〜８で得た炭化材料を、水蒸気流量５ｍｌ、窒素流量２ｌ/分の流速で流通されるロータリーキルン炉の混合ガス雰囲気下、８５０℃で２時間処理して賦活し、活性炭を得た。得られた活性炭について、比表面積をＱＵＡＮＴＡＣＨＲＯＭＥ社製比表面積測定装置「ＮＯＶＥ２０００」により、ＢＥＴ多点法で測定し、また充てん密度をＪＩＳ Ｋ １４７４に準拠して測定した。結果を表４に示す。
(Examples 13-14 and Comparative Examples 13-14)
The carbonized materials obtained in Examples 7 to 8 and Comparative Examples 7 to 8 were activated by treating them at 850 ° C. for 2 hours in a mixed gas atmosphere of a rotary kiln furnace circulated at a water flow rate of 5 ml and a nitrogen flow rate of 2 l / min. Activated carbon was obtained. About the obtained activated carbon, the specific surface area was measured with the specific surface area measuring apparatus "NOVE2000" by QUANTACHROME by the BET multipoint method, and the packing density was measured based on JISK1474. The results are shown in Table 4.
また、上記のようにして得た活性炭を１質量部とり、活性炭に対して１．０質量％の割合でカーボンナノチューブ（昭和電工（株）製「ＶＧＣＦ−Ｈ」）を加えた後に、３０質量％濃度の硫酸を１．５質量部含浸して混練し、ペースト状にした。このペースト０．９ｇを直径３０ｍｍの円形の二枚の白金電極にそれぞれ塗付し、ポリプロピレン製セパレータを介して両電極を圧密着することによって、電気二重層キャパシタを製造した。 Moreover, after taking 1 mass part of activated carbon obtained as mentioned above and adding a carbon nanotube (Showa Denko Co., Ltd. product "VGCF-H") in the ratio of 1.0 mass% with respect to activated carbon, it is 30 mass. The mixture was impregnated with 1.5 parts by mass of sulfuric acid having a concentration of% and kneaded to obtain a paste. An electric double layer capacitor was manufactured by applying 0.9 g of this paste to each of two circular platinum electrodes having a diameter of 30 mm and pressing the electrodes together through a polypropylene separator.
そしてこの実施例１３〜１４及び比較例１３〜１４の電気二重層キャパシタに０．９Ｖで１時間充電した後、放電電流１０ｍＡの放電を行ない、電気二重層キャパシタの電圧が０．５４〜０．４５Ｖまで低下するのに要した時間を測定し、単位時間当たりの静電容量である重量静電容量と単位体積当りの静電容量である容量静電容量を求めた。結果を表４に示す。 Then, after charging the electric double layer capacitors of Examples 13 to 14 and Comparative Examples 13 to 14 at 0.9 V for 1 hour, a discharge current of 10 mA was discharged, and the voltage of the electric double layer capacitor was 0.54 to 0.0. The time required to drop to 45 V was measured, and the weight capacitance, which is the capacitance per unit time, and the capacitance capacitance, which is the capacitance per unit volume, were determined. The results are shown in Table 4.
表４にみられるように、各実施例のものは、比表面積が大きく、静電容量が大きいことが確認される。 As can be seen in Table 4, it is confirmed that each example has a large specific surface area and a large capacitance.
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