JPH05279011A - Production of hydrophobic aerosol - Google Patents
Production of hydrophobic aerosolInfo
- Publication number
- JPH05279011A JPH05279011A JP4255085A JP25508592A JPH05279011A JP H05279011 A JPH05279011 A JP H05279011A JP 4255085 A JP4255085 A JP 4255085A JP 25508592 A JP25508592 A JP 25508592A JP H05279011 A JPH05279011 A JP H05279011A
- Authority
- JP
- Japan
- Prior art keywords
- group
- hydrophobic
- polymer
- gel
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000000443 aerosol Substances 0.000 title abstract 3
- 229920000642 polymer Polymers 0.000 claims abstract description 85
- 125000005372 silanol group Chemical group 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 139
- 239000002904 solvent Substances 0.000 claims description 59
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 48
- 238000000352 supercritical drying Methods 0.000 claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 239000002612 dispersion medium Substances 0.000 claims description 30
- 239000001569 carbon dioxide Substances 0.000 claims description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006068 polycondensation reaction Methods 0.000 claims description 14
- 239000004964 aerogel Substances 0.000 claims description 13
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 125000001165 hydrophobic group Chemical group 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002609 medium Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- -1 silane compound Chemical class 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- DFJDZTPFNSXNAX-UHFFFAOYSA-N ethoxy(triethyl)silane Chemical compound CCO[Si](CC)(CC)CC DFJDZTPFNSXNAX-UHFFFAOYSA-N 0.000 claims description 2
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 claims description 2
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 12
- 230000032683 aging Effects 0.000 abstract description 8
- 230000006866 deterioration Effects 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 206010053317 Hydrophobia Diseases 0.000 abstract 1
- 206010037742 Rabies Diseases 0.000 abstract 1
- 239000000413 hydrolysate Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000203 mixture Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000002834 transmittance Methods 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001879 gelation Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011240 wet gel Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000012814 acoustic material Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、断熱性等、多孔質材
料に特有の機能や、光透過性等に優れ、かつ、疎水性を
有するエアロゲルを製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aerogel which is excellent in functions such as heat insulation and peculiar to a porous material, light transmittance and the like and which is hydrophobic.
【０００２】[0002]
【従来の技術】熱伝導率が小さいため断熱性を有し、か
つ、光透過性を有する材料として、シリカからなるエア
ロゲルが知られている。このようなエアロゲルを製造す
る方法としては、たとえば、アルコキシシラン（シリコ
ンアルコキシド、アルキルシリケート等とも称される）
を加水分解し縮重合して、骨格が（ＳｉＯ2)m で、か
つ、シラノール基を有するポリマーを生成させ、このポ
リマーと、アルコール、液化二酸化炭素等の分散媒とを
含むゲルを、前記分散媒の超臨界条件下で乾燥する（超
臨界乾燥する）方法がある（米国特許第４４０２９２７
号、同４４３２９５６号、同４６１０８６３号の各明細
書等参照）。2. Description of the Related Art Airgel made of silica is known as a material having a heat insulating property and a light transmitting property because of its low thermal conductivity. As a method for producing such an airgel, for example, alkoxysilane (also referred to as silicon alkoxide, alkyl silicate, etc.)
Is hydrolyzed and polycondensed to produce a polymer having a skeleton of (SiO 2 ) m and a silanol group, and a gel containing the polymer and a dispersion medium such as alcohol or liquefied carbon dioxide is dispersed in the dispersion. There is a method of drying (supercritical drying) the medium under supercritical conditions (US Pat. No. 4,402,927).
Nos. 4,432,956 and 4,610,863).
【０００３】[0003]
【発明が解決しようとする課題】ところが、前述の従来
法により得られたエアロゲルは、雰囲気中の水分を表面
に吸着して親水性の高いシラノール基を形成するため、
雰囲気中の水分を経時的に吸着し、その結果、光透過性
や断熱性等の光学的、熱的な初期特性が低下し、さらに
は水分の吸着に起因する収縮によって寸法の変化や割れ
等が生じて、品質や性能が劣化するので、実用上、問題
があった。However, since the airgel obtained by the above-mentioned conventional method adsorbs moisture in the atmosphere on the surface to form a highly hydrophilic silanol group,
Moisture in the atmosphere is adsorbed over time, and as a result, optical and thermal initial properties such as light transmittance and heat insulation are degraded, and further, dimensional changes and cracks due to contraction due to adsorption of water. Occurs, and the quality and performance deteriorate, which is a problem in practical use.
【０００４】このような事情に鑑み、この発明は、水分
等を吸着しにくく、経時的な劣化の少ない、光透過性を
有する多孔体を得ることができる疎水性エアロゲルの製
造方法を提供することを課題とする。In view of such circumstances, the present invention provides a method for producing a hydrophobic aerogel, which makes it possible to obtain a porous body which is less likely to adsorb moisture and the like and is less deteriorated with time, and which has a light-transmitting property. Is an issue.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するた
め、この発明にかかる疎水性エアロゲルの製造方法は、
骨格が（ＳｉＯ2)m （ｍは正の整数）で、かつ、シラノ
ール基を有するポリマーを、前記シラノール基に対して
反応可能な官能基と疎水基を併せ持つ疎水化処理剤と反
応させて疎水化処理することにより得られた変性ポリマ
ーのゲルを超臨界乾燥させて疎水性エアロゲルを得るよ
うにするものである。In order to solve the above problems, a method for producing a hydrophobic airgel according to the present invention is
A polymer having a skeleton of (SiO 2 ) m (m is a positive integer) and having a silanol group is made hydrophobic by reacting with a hydrophobizing agent having both a functional group capable of reacting with the silanol group and a hydrophobic group. The modified polymer gel obtained by the chemical treatment is supercritically dried to obtain a hydrophobic aerogel.
【０００６】この発明の製造方法により得られる疎水性
エアロゲルは、光透過性を有する多孔体である。ここ
で、疎水性とは、たとえば、撥水性と同義であり、水分
吸着等が起こらず、このため、水分による性能劣化がな
いものである。エアロゲル（エーロゲル）は、一般に
は、湿潤アルコゲル等、乾燥前の分散媒を含んだ状態で
のゲル体から分散媒などを除去して得られる多孔質な材
料を指し、超臨界抽出により分散媒を除去して得られる
乾燥多孔質ゲルを含む。The hydrophobic airgel obtained by the production method of the present invention is a light-transmitting porous body. Here, the hydrophobicity is synonymous with, for example, water repellency, and does not cause moisture adsorption or the like, and therefore does not cause performance deterioration due to moisture. Aerogel generally refers to a porous material obtained by removing a dispersion medium or the like from a gel body containing a dispersion medium before drying, such as a wet alcogel, and a dispersion medium obtained by supercritical extraction. It includes a dry porous gel obtained by removal.
【０００７】この発明において、疎水化処理剤と反応さ
せて疎水化処理されるポリマーは、その骨格が少なくと
も（ＳｉＯ2)m で、かつ、シラノール基を有するケイ酸
化合物である。このものは、分子中に、Ｓｉ−Ｒ1 で表
される結合を含有していてもよい。ここで、ｍは正の整
数で、Ｒ1 は炭素数１〜５のアルキル基またはフェニル
基である。このポリマーを構成するＳｉは、雰囲気中の
水分を吸着し、シラノール基を形成して安定化する傾向
が極めて強い性質がある。In the present invention, the polymer hydrophobized by reacting with the hydrophobizing agent is a silicic acid compound having a skeleton of at least (SiO 2 ) m and a silanol group. This thing may contain the bond represented by Si-R < 1 > in the molecule. Here, m is a positive integer, and R 1 is an alkyl group having 1 to 5 carbon atoms or a phenyl group. Si which constitutes this polymer has a property that it has a very strong tendency to adsorb moisture in the atmosphere and form silanol groups to stabilize it.
【０００８】このような性質を有する（ＳｉＯ2)m を骨
格とするポリマーとしては、特に限定はされないが、た
とえば、下記一般式（Ｉ）で表されるアルコキシシラン
を加水分解し、縮重合して得られたもの等が挙げられ
る。 ＳｉＲ1 n （ＯＲ2)4-n …（Ｉ） 〔式（Ｉ）中、Ｒ1 およびＲ2 は、互いに独立に、炭素
数１〜５のアルキル基またはフェニル基を表し、ｎは０
〜２の整数である。Ｒ1 およびＲ2 がそれぞれ２個以上
ある場合、２個以上のＲ1 、２個以上のＲ2 は、それぞ
れ、互いに同じであってもよく、異なっていてもよ
い。〕上記一般式（Ｉ）で表されるアルコキシシランと
しては、より具体的には、下記一般式（II）で表される
２官能アルコキシシラン、下記一般式（III)で表される
３官能アルコキシシランおよび下記一般式（IV）で表さ
れる４官能アルコキシシランのうちの少なくとも１種が
用いられる。The polymer having a (SiO 2 ) m skeleton having such properties is not particularly limited, but for example, an alkoxysilane represented by the following general formula (I) is hydrolyzed and polycondensed. And the like. SiR 1 n (OR 2) 4 -n ... (I) wherein (I), R 1 and R 2 each independently represents an alkyl group or a phenyl group having 1 to 5 carbon atoms, n represents 0
Is an integer of ˜2. When each of R 1 and R 2 is 2 or more, 2 or more R 1 and 2 or more R 2 may be the same or different from each other. As the alkoxysilane represented by the general formula (I), more specifically, a bifunctional alkoxysilane represented by the following general formula (II) and a trifunctional alkoxysilane represented by the following general formula (III). At least one of silane and a tetrafunctional alkoxysilane represented by the following general formula (IV) is used.
【０００９】 〔式（II）中、Ｒ3 、Ｒ4 およびＲ5 は、互いに独立
に、炭素数１〜５のアルキル基またはフェニル基を表
す。２個のＲ5 は、互いに同じであってもよく、異なっ
ていてもよい。〕 Ｒ6 −Ｓｉ (ＯＲ7)3 …（III) 〔式（III)中、Ｒ6 およびＲ7 は、互いに独立に、炭素
数１〜５のアルキル基またはフェニル基を表す。３個の
Ｒ7 は、互いに同じであってもよく、異なっていてもよ
い。〕 Ｓｉ (ＯＲ8)4 …（IV） 〔式（IV）中、Ｒ8 は、炭素数１〜５のアルキル基また
はフェニル基を表す。４個のＲ8 は互いに同じであって
もよく、異なっていてもよい。〕で表される４官能アル
コキシシラン、上記式（II）、（III)および（IV）でそ
れぞれ表される２官能、３官能および４官能の各アルコ
キシシランとしては、特に限定されないが、それらの具
体例を挙げると、２官能アルコキシシランとしては、た
とえば、ジメチルジメトキシシラン、ジメチルジエトキ
シシラン、ジフェニルジエトキシシラン、ジフェニルジ
メトキシシラン、メチルフェニルジエトキシシラン、メ
チルフェニルジメトキシシラン、ジエチルジエトキシシ
ラン、ジエチルジメトキシシラン等が用いられる。３官
能アルコキシシランとしては、たとえば、メチルトリメ
トキシシラン、メチルトリエトキシシラン、エチルトリ
メトキシシラン、エチルトリエトキシシラン、フェニル
トリメトキシシラン、フェニルトリエトキシシラン等が
用いられる。４官能アルコキシシランとしては、たとえ
ば、テトラメトキシシラン、テトラエトキシシラン等が
用いられる。[0009] [In the formula (II), R 3 , R 4 and R 5 independently represent an alkyl group having 1 to 5 carbon atoms or a phenyl group. The two R 5 s may be the same as or different from each other. ] In R 6 -Si (OR 7) 3 ... (III) [Formula (III), R 6 and R 7 independently of one another represent an alkyl group or a phenyl group having 1 to 5 carbon atoms. The three R 7 s may be the same or different from each other. ] In Si (OR 8) 4 ... ( IV) [Formula (IV), R 8 is an alkyl group or a phenyl group having 1 to 5 carbon atoms. The four R 8 may be the same as or different from each other. The tetrafunctional alkoxysilane represented by the following formula and the bifunctional, trifunctional and tetrafunctional alkoxysilanes represented by the above formulas (II), (III) and (IV) are not particularly limited, but Specific examples include bifunctional alkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldimethoxysilane, diethyldiethoxysilane, and diethyl. Dimethoxysilane or the like is used. As the trifunctional alkoxysilane, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane and the like are used. As the tetrafunctional alkoxysilane, for example, tetramethoxysilane, tetraethoxysilane or the like is used.
【００１０】前記一般式（Ｉ）で表されるアルコキシシ
ラン（以下、特に断らない限り「アルコキシシラン」は
このものを指す。）を効率良く加水分解し、縮重合を行
うためには、アルコキシシランを含む反応系に予め触媒
を添加しておくことが好ましい。このような触媒として
は、酸性触媒、塩基性触媒等が挙げられる。具体的に述
べると、酸性触媒としては、塩酸、クエン酸、硝酸、硫
酸、フッ化アンモニウム等が用いられ、塩基性触媒とし
ては、アンモニア、ピペリジン等が用いられるが、これ
らに限定されるものではない。In order to efficiently hydrolyze the alkoxysilane represented by the general formula (I) (hereinafter, "alkoxysilane" refers to this unless otherwise specified) to perform polycondensation, alkoxysilane is used. It is preferable to add a catalyst in advance to the reaction system containing Examples of such catalysts include acidic catalysts and basic catalysts. Specifically, as the acidic catalyst, hydrochloric acid, citric acid, nitric acid, sulfuric acid, ammonium fluoride or the like is used, and as the basic catalyst, ammonia, piperidine or the like is used, but is not limited to these. Absent.
【００１１】アルコキシシランの加水分解と縮重合は、
水との相溶性を有し、かつ、アルコキシシランを溶解す
る溶媒と、水との混合液を用いて行うことが好ましい。
このような混合液を用いた場合、加水分解工程と縮重合
工程を連続して行うことができ、効率が良いからであ
る。その際、生成するポリマーは、上記溶媒を分散媒と
するゲル化物として得られる。水との相溶性を有し、か
つ、アルコキシシランを溶解する溶媒としては、特に限
定はされないが、たとえば、メタノール、エタノール、
プロパノール、イソプロパノール、ブタノール等のアル
コールや、アセトン、Ｎ，Ｎ−ジメチルホルムアミド等
が挙げられる。これらは、１種のみを用いてもよいし、
２種以上を併用してもよい。Hydrolysis and polycondensation of alkoxysilanes
It is preferable to use a mixed solution of water and a solvent that is compatible with water and dissolves the alkoxysilane.
When such a mixed solution is used, the hydrolysis step and the polycondensation step can be continuously performed, and the efficiency is good. At that time, the produced polymer is obtained as a gelled product using the solvent as a dispersion medium. The solvent having compatibility with water and dissolving the alkoxysilane is not particularly limited, but for example, methanol, ethanol,
Examples thereof include alcohols such as propanol, isopropanol and butanol, and acetone and N, N-dimethylformamide. These may use only 1 type,
You may use 2 or more types together.
【００１２】次に、骨格が（ＳｉＯ2)m （ｍは正の整
数）で、かつ、シラノール基を有するポリマー（以下、
これを「原料ポリマー」と称することがある）を疎水化
処理剤と反応させて疎水化処理する工程について説明す
る。原料ポリマーは、必要に応じて、疎水化処理を効率
良く行うために予め水分を除去されたものであることが
好ましい。原料ポリマーの水分除去は、特に、ポリマー
が、アルコキシシランを加水分解し、縮重合を行うこと
により得られたポリマーである場合に有効である。原料
ポリマーの水分を除去する方法としては、特に限定はさ
れないが、たとえば、アルコキシシランを加水分解し、
縮重合を行う際に用いられる溶媒として前述した溶媒で
ポリマーを洗浄する方法等が挙げられる。Next, a polymer having a skeleton of (SiO 2 ) m (m is a positive integer) and having a silanol group (hereinafter, referred to as
This may be referred to as a "raw material polymer") with a hydrophobizing agent to perform a hydrophobizing treatment. The raw material polymer is preferably one from which water has been removed in advance in order to efficiently carry out the hydrophobic treatment, if necessary. The removal of water from the raw material polymer is particularly effective when the polymer is a polymer obtained by hydrolyzing an alkoxysilane and conducting polycondensation. The method of removing the water content of the raw material polymer is not particularly limited, for example, by hydrolyzing an alkoxysilane,
Examples of the solvent used for the condensation polymerization include a method of washing the polymer with the above-mentioned solvent.
【００１３】この発明で用いられる疎水化処理剤は、原
料ポリマーの有するシラノール基に対して反応可能な官
能基と、疎水基とを併せ持つ化合物である。シラノール
基に対して反応可能な官能基としては、特に限定はされ
ないが、たとえば、ハロゲン、アミノ基、イミノ基、カ
ルボキシル基およびアルコキシル基等が挙げられる。疎
水基としては、特に限定はされないが、たとえば、アル
キル基、フェニル基およびそれらのフッ化物等が挙げら
れる。疎水化処理剤は、上記の官能基および疎水基を、
それぞれ、１種のみ有していてもよいし、２種以上有し
ていてもよい。疎水化処理剤の具体例としては、たとえ
ば、ヘキサメチルジシラザン、ヘキサメチルジシロキサ
ン、トリメチルクロロシラン、トリメチルメトキシシラ
ン、トリメチルエトキシシラン、トリエチルエトキシシ
ラン、トリエチルメトキシシラン、ジメチルジクロロシ
ラン、ジメチルジエトキシシラン、ジエチルジエトキシ
シラン、メチルトリクロロシランおよびエチルトリクロ
ロシラン等のシラン化合物が挙げられるが、これらに限
定されない。すなわち、シラン化合物以外の化合物、た
とえば、蟻酸、酢酸、コハク酸等のカルボン酸や、メチ
ルクロリド等のハロゲン化アルキル等であってもよいの
である。疎水化処理剤は、１種のみを用いてもよいし、
２種以上を併用してもよい。The hydrophobizing agent used in the present invention is a compound having both a functional group capable of reacting with the silanol group of the raw material polymer and a hydrophobic group. The functional group capable of reacting with the silanol group is not particularly limited, but examples thereof include a halogen, an amino group, an imino group, a carboxyl group and an alkoxyl group. The hydrophobic group is not particularly limited, but examples thereof include an alkyl group, a phenyl group and their fluorides. The hydrophobizing agent has the above-mentioned functional group and hydrophobic group,
Each may have only one type, or may have two or more types. Specific examples of the hydrophobic treatment agent, for example, hexamethyldisilazane, hexamethyldisiloxane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triethylmethoxysilane, dimethyldichlorosilane, dimethyldiethoxysilane, Examples include, but are not limited to, silane compounds such as diethyldiethoxysilane, methyltrichlorosilane and ethyltrichlorosilane. That is, it may be a compound other than the silane compound, for example, a carboxylic acid such as formic acid, acetic acid, succinic acid, or an alkyl halide such as methyl chloride. Only one kind of hydrophobic treatment agent may be used,
You may use 2 or more types together.
【００１４】疎水化処理を行う手法としては、特に限定
はされないが、たとえば、疎水化処理剤を溶媒に溶解さ
せた溶液中に原料ポリマーを浸漬し、混合するなどして
原料ポリマー内に疎水化処理剤を浸透させた後、必要に
応じて加熱し、疎水化処理反応を行う方法等が挙げられ
る。疎水化処理時に用いる溶媒としては、たとえば、エ
タノール、メタノール、トルエン、ベンゼン、Ｎ，Ｎ−
ジメチルホルムアミド等が挙げられるが、前記疎水化処
理剤が容易に溶解し、かつ、原料ポリマーの含有する溶
媒（分散媒）と置換可能なものであれば、上記に限定さ
れるものではない。また、後で超臨界乾燥を行うため、
超臨界乾燥の容易な溶媒（たとえば、エタノール、メタ
ノール、液体ＣＯ2 等）と同一種類もしくはそれとの置
換が容易なものの方が好ましい。The method for carrying out the hydrophobizing treatment is not particularly limited, but for example, the raw material polymer is immersed in a solution in which the hydrophobizing agent is dissolved in a solvent and mixed to make the raw material polymer hydrophobic. After permeating the treatment agent, a method of heating as necessary to carry out a hydrophobization treatment reaction and the like can be mentioned. Examples of the solvent used in the hydrophobic treatment include ethanol, methanol, toluene, benzene, N, N-
Examples thereof include dimethylformamide, but the hydrophobic treatment agent is not limited to the above as long as it can be easily dissolved and can be replaced with the solvent (dispersion medium) contained in the raw material polymer. In addition, since the supercritical drying is performed later,
A solvent that is easily supercritically dried (for example, ethanol, methanol, liquid CO 2 or the like) and a solvent that is easily replaced with the same type is preferable.
【００１５】疎水化処理は、原料ポリマーの有するシラ
ノール基の水酸基を、疎水化処理剤の有する官能基と反
応させて疎水化するために行うものである。したがっ
て、疎水化処理剤の使用量としては、原料ポリマーの粒
子表面のシラノール基数に対して充分になる量用いるこ
とが好ましい。たとえば、重量比で（原料ポリマー）／
（疎水化処理剤）＝０．５〜１０程度の範囲が好ましい
が、これは、疎水化処理反応を行う溶媒量、温度、時間
等や、また、コストと性能の兼ね合い等から選択できる
ため、限定されない。また、溶媒の使用量としても限定
されない。The hydrophobizing treatment is carried out in order to hydrophobize the hydroxyl group of the silanol group of the raw material polymer by reacting it with the functional group of the hydrophobizing agent. Therefore, it is preferable to use the hydrophobizing agent in an amount sufficient for the number of silanol groups on the particle surface of the raw material polymer. For example, by weight ratio (raw polymer) /
The range of (hydrophobizing agent) = 0.5 to 10 is preferable, but this can be selected from the amount of solvent for performing the hydrophobizing reaction, temperature, time, and the like, and the balance between cost and performance. Not limited. Also, the amount of solvent used is not limited.
【００１６】上に述べた疎水化処理により得られる変性
ポリマーは、原料ポリマーの有するシラノール基の水酸
基が疎水基で置換されて疎水化したものであり、ポリマ
ー固形分と分散媒との２相からなるゲルとして得られ
る。この場合の分散媒とは、前述した、原料ポリマーの
調製時に用いられる溶媒や疎水化処理時に用いられる溶
媒、あるいは、後述の超臨界乾燥に適した他の溶媒のこ
とであり、この明細書中では、ゲルを構成する液相を分
散媒と記すが、広義では溶媒と同義である。The modified polymer obtained by the above-mentioned hydrophobization treatment is one in which the hydroxyl group of the silanol group of the raw material polymer is replaced with a hydrophobic group to make it hydrophobic, and the polymer solid content and the dispersion medium form two phases. It is obtained as a gel. The dispersion medium in this case is the above-mentioned solvent used in the preparation of the raw material polymer, the solvent used in the hydrophobizing treatment, or another solvent suitable for the supercritical drying described below. Then, the liquid phase constituting the gel is described as a dispersion medium, but in a broad sense, it is synonymous with a solvent.
【００１７】次に、上記変性ポリマーのゲルを超臨界乾
燥する工程について説明する。ここで、超臨界乾燥と
は、ゲルに含まれている分散媒（溶媒）の臨界点または
臨界点よりも高温高圧の雰囲気中で分散媒を徐々に除去
する乾燥法である。超臨界乾燥を行う際には、必要に応
じて、変性ポリマーのゲル中の分散媒を、超臨界乾燥の
媒体として用いる分散媒に予め置換しておく。その際、
超臨界乾燥の媒体として用いる分散媒は、変性ポリマー
のゲル中の分散媒よりも臨界点の低い化合物からなるも
のを用いることが好ましいが、これに限定されない。た
とえば、疎水化処理時の溶媒を超臨界乾燥の媒体として
そのまま用いてもよく、その場合は、分散媒（溶媒）の
置換操作を行う必要はない。Next, the step of supercritically drying the gel of the modified polymer will be described. Here, the supercritical drying is a drying method in which the dispersion medium is gradually removed in the atmosphere at a critical point of the dispersion medium (solvent) contained in the gel or at a temperature and pressure higher than the critical point. When performing supercritical drying, the dispersion medium in the gel of the modified polymer is replaced with a dispersion medium used as a medium for supercritical drying in advance, if necessary. that time,
The dispersion medium used as a medium for supercritical drying is preferably, but not limited to, a compound having a lower critical point than the dispersion medium in the gel of the modified polymer. For example, the solvent used for the hydrophobizing treatment may be used as it is as a medium for supercritical drying, and in that case, it is not necessary to perform the replacement operation of the dispersion medium (solvent).
【００１８】超臨界乾燥の媒体として用いられる分散媒
（溶媒）としては、臨界点以上の温度圧力の設定が容易
なものが好ましいが、これに限定されない。具体的に
は、たとえば、メタノール、エタノール、プロパノー
ル、イソプロパノール、ブタノール等のアルコールや、
ジクロロジフルオロメタン、液化二酸化炭素、水等の単
独系または２種以上の混合系を挙げることができる。超
臨界乾燥の媒体として用いられる分散媒は、前述したア
ルコキシシランの加水分解と縮重合を行う際に用いられ
る溶媒（水との相溶性を有し、かつ、アルコキシシラン
を溶解する溶媒）もしくは疎水化処理時に用いられる溶
媒と同一種類のものを用いてもよいし、それらと異なる
種類のものを用いてもよい。As the dispersion medium (solvent) used as a medium for supercritical drying, it is preferable that the temperature and pressure above the critical point can be easily set, but the dispersion medium (solvent) is not limited to this. Specifically, for example, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and the like,
Examples include dichlorodifluoromethane, liquefied carbon dioxide, water and the like alone or as a mixture of two or more kinds. The dispersion medium used as a medium for supercritical drying is a solvent (solvent that has compatibility with water and dissolves alkoxysilane) or hydrophobic solvent used in the hydrolysis and condensation polymerization of the alkoxysilane described above. The same type of solvent as that used in the chemical treatment may be used, or a different type of solvent may be used.
【００１９】超臨界乾燥を行う際に用いられる容器とし
ては、特に限定はされないが、除去される分散媒の臨界
点以上の高温高圧に耐えられる容器が好ましく、たとえ
ば、オートクレーブ等が挙げられる。この発明の疎水性
エアロゲルの製造方法は、特に限定されるわけではない
が、たとえば、以下のようにして行われる。The container used for supercritical drying is not particularly limited, but a container capable of withstanding high temperature and high pressure above the critical point of the dispersion medium to be removed is preferable, and examples thereof include an autoclave. The method for producing the hydrophobic airgel of the present invention is not particularly limited, but is performed as follows, for example.
【００２０】まず、アルコキシシランにアルコール、
水、および、必要に応じて触媒を添加混合し、アルコキ
シシランを加水分解し、縮重合させる。縮重合反応が充
分に進行すると、反応混合物がゲル化する。次に、この
ゲル化物にアルコールを添加し、加熱する、いわゆる熟
成を行う。なお、この際、必要に応じては、熟成工程を
省いても良い。アルコールを添加した場合には、湿潤ア
ルコゲルが得られる。First, the alkoxysilane is alcohol,
Water and, if necessary, a catalyst are added and mixed to hydrolyze the alkoxysilane to cause polycondensation. When the polycondensation reaction proceeds sufficiently, the reaction mixture gels. Next, so-called aging is performed by adding alcohol to this gelled product and heating it. At this time, the aging step may be omitted if necessary. If alcohol is added, a wet alcogel is obtained.
【００２１】湿潤アルコゲル等のゲル化物（原料ポリマ
ーのゲル）を疎水化処理剤と反応させて疎水化処理す
る。この疎水化処理のための反応は、たとえば、原料ポ
リマーのゲル化物中に含まれるアルコールを、疎水化処
理剤を溶媒に溶解させた処理液と置換し、必要に応じ加
熱して行われる。反応後、たとえば、再びアルコールで
溶媒の置換を行ってから、超臨界乾燥を行う。なお、疎
水化処理剤を溶解させた処理液の溶媒としては、疎水化
処理剤に対する溶解性がアルコールよりも高いものを用
いることが好ましく、また、沸点がアルコールよりも高
いものを用いることが好ましい。沸点がアルコールより
も高い溶媒としては、アルコールの種類により異なる
が、たとえば、トルエン等が挙げられる。A gelled substance such as wet alcogel (gel of raw material polymer) is reacted with a hydrophobizing agent to be hydrophobized. The reaction for the hydrophobizing treatment is carried out, for example, by replacing the alcohol contained in the gelled product of the raw material polymer with a treatment liquid prepared by dissolving the hydrophobizing treating agent in a solvent, and heating as necessary. After the reaction, for example, the solvent is replaced with alcohol again, and then supercritical drying is performed. As the solvent of the treatment liquid in which the hydrophobizing agent is dissolved, it is preferable to use one having a higher solubility in the hydrophobizing agent than alcohol, and it is preferable to use one having a boiling point higher than that of alcohol. .. The solvent having a boiling point higher than that of alcohol varies depending on the type of alcohol, and examples thereof include toluene.
【００２２】上記の疎水化処理により得られた変性ポリ
マーのゲルを超臨界乾燥させる方法としては、特に限定
されないが、たとえば、変性ポリマーのゲルを液化二酸
化炭素（５０〜６０気圧程度）中に浸漬して、ゲルの含
むアルコールの全部または一部を、このアルコールより
も臨界点が低い液化二酸化炭素に置換した後、二酸化炭
素の単独系、または、二酸化炭素とアルコールとの混合
系の超臨界条件下で乾燥する方法、あるいは、二酸化炭
素との置換を行わず、溶媒として使用しているアルコー
ルの超臨界条件下で乾燥する方法等が挙げられる。The method of supercritically drying the gel of the modified polymer obtained by the above hydrophobic treatment is not particularly limited, but for example, the gel of the modified polymer is immersed in liquefied carbon dioxide (about 50 to 60 atm). Then, after replacing all or part of the alcohol contained in the gel with liquefied carbon dioxide having a lower critical point than this alcohol, a single system of carbon dioxide or a supercritical condition of a mixed system of carbon dioxide and alcohol. Examples thereof include a method of drying below, or a method of performing drying under supercritical conditions of alcohol used as a solvent without performing substitution with carbon dioxide.
【００２３】このような超臨界乾燥を行い、変性ポリマ
ーの含有する流体を除去することにより、優れた疎水性
が付与された光透過性を有するエアロゲル（多孔体）が
得られる。また、上記のようにして湿潤ゲル時に疎水化
処理を施しておくと、その超臨界乾燥時の寸法収縮は全
く無く、溶媒を除去して得られるエアロゲルは軽量で、
非常に性能（断熱性等）の優れたものとなる。By carrying out such supercritical drying and removing the fluid containing the modified polymer, an airgel (porous body) having excellent light-transmitting properties and having a light-transmitting property is obtained. Further, if the hydrophobic treatment is performed during the wet gel as described above, there is no dimensional shrinkage at the time of supercritical drying, and the airgel obtained by removing the solvent is lightweight,
The performance (insulation, etc.) will be extremely excellent.
【００２４】[0024]
【作用】骨格が（ＳｉＯ2)m で、かつ、シラノール基を
有するポリマー（原料ポリマー）を、前記シラノール基
に対して反応可能な官能基と疎水基を併せ持つ疎水化処
理剤と反応させて疎水化処理することにより得られた変
性ポリマーのゲルを超臨界乾燥させるようにすると、水
分等を吸着しにくく、経時的な劣化の少ない、光透過性
を有するエアロゲルを得ることが可能になる。[Function] A polymer having a skeleton of (SiO 2 ) m and having a silanol group (raw material polymer) is reacted with a hydrophobizing agent having both a functional group capable of reacting with the silanol group and a hydrophobic group to make it hydrophobic. By subjecting the gel of the modified polymer obtained by the chemical treatment to the supercritical drying, it is possible to obtain an airgel which is less likely to adsorb moisture and the like and has less deterioration over time and which has optical transparency.
【００２５】ゲル化物に含まれている溶媒（分散媒）の
臨界点または臨界点よりも高温高圧の雰囲気中すなわち
超臨界状態では溶媒の相転移（気化、凝縮）が起こらな
いため、このような超臨界状態で乾燥を行うと、溶媒除
去時のゲル化物の構造体の破壊、凝集が抑制される。こ
のため、超臨界乾燥によって得られたエアロゲルは、多
孔質なものとなる。これに対し通常の加熱乾燥では、溶
媒が液体から気体に変化するため、ゲル化物の構造体中
から除去される際に、溶媒の表面エネルギーによって前
記構造体が破壊されたり、凝集したりする。Since the solvent does not undergo phase transition (vaporization, condensation) in the supercritical state, that is, in the atmosphere at a critical point of the solvent (dispersion medium) contained in the gelled substance or at a temperature higher than the critical point, that is, in the supercritical state, When the drying is carried out in the supercritical state, the destruction and aggregation of the gelled structure at the time of removing the solvent is suppressed. Therefore, the airgel obtained by supercritical drying becomes porous. On the other hand, in ordinary heating and drying, since the solvent changes from a liquid to a gas, when the gelled product is removed from the structure, the surface energy of the solvent causes the structure to be destroyed or aggregated.
【００２６】しかし、もしも、疎水化処理を施さずにゲ
ル体の超臨界乾燥を行うと、若干（数％）の収縮が起こ
る。この理由は次のように考えられる。原料ポリマーの
構成体であるシリカ微粒子は粒子表面に非常に多くのシ
ラノール基を有している。従って、シラノール基同士、
または、湿潤ゲル状態の時から微量に存在しうる水分と
シラノール基による水素結合が起こっており、乾燥時末
期にはこれらの張力によって粒子結合力は増し、若干の
収縮が起こる。However, if the gel body is supercritically dried without being subjected to the hydrophobizing treatment, some (several percent) shrinkage occurs. The reason for this is considered as follows. The silica fine particles, which are the constituents of the raw material polymer, have very many silanol groups on the particle surface. Therefore, silanol groups,
Alternatively, a small amount of water, which may be present in the wet gel state, and hydrogen bonds due to silanol groups have occurred, and at the end of the drying period, these tensions increase the particle binding force and cause some shrinkage.
【００２７】ところが、この発明のように、原料ポリマ
ーの構成微粒子を疎水化処理すると、乾燥時の上記のよ
うなシラノール基による影響はないため、超臨界乾燥を
行うと、微細な多孔質構造を維持できるように理想的に
溶媒が除去できる。このため、この発明は、エアロゲル
の空孔径やかさ密度の設計が容易であったり、または、
かさ密度の小さなものを作製するのに有利であったりす
るという利点を有する。However, when the constituent fine particles of the raw material polymer are subjected to the hydrophobic treatment as in the present invention, there is no influence of the silanol group as described above during the drying. Therefore, when supercritical drying is performed, a fine porous structure is formed. Ideally the solvent can be removed so that it can be maintained. Therefore, the present invention is easy to design the pore size and bulk density of the airgel, or,
It has an advantage that it is advantageous for producing a product having a low bulk density.
【００２８】この発明の製造方法により得られたエアロ
ゲルは、上記したように非常に微細なシリカ粒子からな
る構造体で、その粒子径および粒子間空隙は光の波長よ
りもはるかに小さいために、多孔体であるにもかかわら
ず光透過性を有する。また、ゲル化物（ゲル体）のシリ
カ粒子に対して、粒子表面が撥水性を有するように疎水
化処理を施すことによって、得られるエアロゲルは優れ
た疎水性を示し、水分等を吸着しにくいため、水分等の
吸着による、断熱性、透明性等の性能劣化を防ぐことが
できる。ここで透明性とは、たとえば、可視光波長領域
等に対する視覚的な透明性であるが、これに限定されな
い。The airgel obtained by the production method of the present invention is a structure composed of extremely fine silica particles as described above, and since the particle diameter and the interparticle void are much smaller than the wavelength of light, Even though it is a porous body, it has optical transparency. Also, by subjecting silica particles of a gelled substance (gel body) to a hydrophobic treatment so that the particle surface has water repellency, the obtained aerogel exhibits excellent hydrophobicity and does not easily adsorb moisture or the like. It is possible to prevent performance deterioration such as heat insulation and transparency due to adsorption of water and the like. Here, the transparency is, for example, visual transparency with respect to a visible light wavelength region and the like, but is not limited thereto.
【００２９】[0029]
【実施例】以下に、この発明の具体的な実施例および比
較例を示すが、この発明は下記実施例に限定されない。 −実施例１− テトラメトキシシラン（東レダウコーニングシリコーン
（株）製試薬）に、エタノール（ナカライテスク（株）
製特級試薬）と０．０１mol/l のアンモニア水溶液とを
混合したものを徐々に添加した。この際、反応は室温で
行い、混合比は、テトラメトキシシラン：エタノール：
アンモニア水＝１：５：４（モル比）であった。２時間
程度攪拌後静置し、ゲル化させた。ゲル化後、エタノー
ルを加え、５０℃で加熱し、さらにエタノールの添加を
繰り返してゲルが乾燥しないように縮重合反応を加速
（熟成）した。EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples. -Example 1-Tetramethoxysilane (a reagent manufactured by Toray Dow Corning Silicone Co., Ltd.) was mixed with ethanol (Nacalai Tesque Co., Ltd.).
A mixture of a special grade reagent) and a 0.01 mol / l aqueous ammonia solution was gradually added. At this time, the reaction is performed at room temperature, and the mixing ratio is tetramethoxysilane: ethanol:
Ammonia water was 1: 5: 4 (molar ratio). After stirring for about 2 hours, the mixture was allowed to stand and gelled. After gelation, ethanol was added and heated at 50 ° C., and the addition of ethanol was repeated to accelerate (age) the polycondensation reaction so that the gel was not dried.
【００３０】次に、このゲル化物をゲルの５倍の容積の
０．２mol/l −トリメチルクロロシラン（東レダウコー
ニングシリコーン（株）製試薬）のトルエン溶液中に移
し、１昼夜この溶媒の交換を繰り返し、ゲル内にトリメ
チルクロロシランを混合した。その後、１１０℃で２時
間程度加熱攪拌し、疎水化処理反応を行った後、今度
は、ゲルをエタノール中に移して、１昼夜、エタノール
の交換を繰り返し、溶媒置換を行った。Next, the gelled product was transferred to a toluene solution of 0.2 mol / l-trimethylchlorosilane (a reagent manufactured by Toray Dow Corning Silicone Co., Ltd.) having a volume five times that of the gel, and the solvent was exchanged overnight. Repeatedly, trimethylchlorosilane was mixed in the gel. Then, the mixture was heated and stirred at 110 ° C. for about 2 hours to carry out a hydrophobizing treatment reaction, and this time, the gel was transferred into ethanol, and the ethanol was repeatedly exchanged for one day and night to carry out solvent replacement.
【００３１】次に、このゲルを１８℃、５５気圧の二酸
化炭素中に入れ、ゲル内のエタノールを二酸化炭素に置
換する操作を２〜３時間行った。その後、系内を二酸化
炭素の超臨界条件である、４０℃、８０気圧にし、超臨
界乾燥を約２４時間行ってエアロゲル試料を得た。試料
の大きさは、厚み５mm、直径５０mmであった。 −実施例２− 実施例１において、トリメチルクロロシランを用いる代
わりにヘキサメチルジシラザン（東レダウコーニングシ
リコーン（株）製試薬）を用いたこと以外は実施例１と
同様にしてエアロゲル試料を得た。Next, this gel was placed in carbon dioxide at 18 ° C. and 55 atm, and the operation of replacing ethanol in the gel with carbon dioxide was carried out for 2 to 3 hours. Then, the system was heated to 40 ° C. and 80 atm, which is a supercritical condition of carbon dioxide, and supercritical drying was performed for about 24 hours to obtain an airgel sample. The size of the sample was 5 mm in thickness and 50 mm in diameter. -Example 2- An airgel sample was obtained in the same manner as in Example 1 except that hexamethyldisilazane (a reagent manufactured by Toray Dow Corning Silicone Co., Ltd.) was used in place of trimethylchlorosilane.
【００３２】−実施例３− 実施例２において、二酸化炭素を媒体とする超臨界乾燥
を行う代わりに、エタノールをエタノールの超臨界条件
下（２５０℃、８０気圧）で超臨界乾燥を行うようにし
たこと以外は実施例２と同様にしてエアロゲル試料を得
た。 −実施例４− 実施例２において、テトラメトキシシランを用いる代わ
りにテトラエトキシシラン（東レダウコーニングシリコ
ーン（株）製試薬）を用い、混合比をテトラエトキシシ
ラン：エタノール：アンモニア水＝１：５．５：５とし
たこと以外は、実施例２と同様にしてエアロゲル試料を
得た。Example 3 In Example 2, instead of performing supercritical drying using carbon dioxide as a medium, ethanol is subjected to supercritical drying under supercritical conditions of ethanol (250 ° C., 80 atm). An airgel sample was obtained in the same manner as in Example 2 except for the above. Example 4 In Example 2, tetraethoxysilane (a reagent manufactured by Toray Dow Corning Silicone Co., Ltd.) was used instead of tetramethoxysilane, and the mixing ratio was tetraethoxysilane: ethanol: ammonia water = 1: 5. An airgel sample was obtained in the same manner as in Example 2 except that the ratio was set to 5: 5.
【００３３】−実施例５− 実施例４において、０．０１mol/l のアンモニア水を用
いる代わりに０．０４mol/l のフッ化アンモニウム水溶
液を用いたこと以外は、実施例４と同様にしてエアロゲ
ル試料を得た。 −実施例６− 実施例１の乾燥工程において、４０℃、８０気圧の条件
で約２４時間の超臨界乾燥を行う代わりに、８０℃、１
６０気圧の条件で約４８時間の超臨界乾燥を行ったこと
以外は、実施例１と同様にしてエアロゲル試料を得た。Example 5-Aerogel similar to Example 4 except that 0.04 mol / l ammonium fluoride aqueous solution was used in place of 0.01 mol / l ammonia water in Example 4. A sample was obtained. -Example 6-In the drying process of Example 1, 80 degreeC, 1 degree instead of performing supercritical drying for about 24 hours on conditions of 40 degreeC and 80 atmospheres.
An airgel sample was obtained in the same manner as in Example 1 except that supercritical drying was performed for about 48 hours under the condition of 60 atm.
【００３４】−実施例７− 実施例１において、テトラメトキシシランの代わりに２
官能アルコキシシランであるジメチルジメトキシシラン
とテトラメトキシシランの１：９（モル比）の混合物を
用いたこと以外は、実施例１と同様にしてエアロゲル試
料を得た。 −実施例８− 実施例１において、テトラメトキシシランの代わりに３
官能アルコキシシランであるメチルトリメトキシシラン
とテトラメトキシシランの５：５（モル比）の混合物を
用いたこと以外は、実施例１と同様にしてエアロゲル試
料を得た。Example 7 In Example 1, 2 instead of tetramethoxysilane was used.
An airgel sample was obtained in the same manner as in Example 1 except that a 1: 9 (molar ratio) mixture of dimethyldimethoxysilane that was a functional alkoxysilane and tetramethoxysilane was used. -Example 8--In Example 1, it replaced with 3 instead of tetramethoxysilane.
An airgel sample was obtained in the same manner as in Example 1 except that a 5: 5 (molar ratio) mixture of methyltrimethoxysilane that was a functional alkoxysilane and tetramethoxysilane was used.
【００３５】−実施例９− 実施例１において、トリメチルクロロシランの代わり
に、トリフロロプロピル−トリメトキシシラン（東レダ
ウコーニングシリコーン（株）製試薬、ＡＸ４３−０１
３）を用いたこと以外は、実施例１と同様にしてエアロ
ゲル試料を得た。 −実施例１０− 実施例２において、テトラメトキシシランを用いる代わ
りにテトラエトキシシラン（東レダウコーニングシリコ
ーン（株）製試薬）を用い、混合比をテトラエトキシシ
ラン：エタノール：アンモニア水＝１：１４：１２とし
たこと以外は、実施例２と同様にしてエアロゲル試料を
得た。Example 9 In Example 1, instead of trimethylchlorosilane, trifluoropropyl-trimethoxysilane (a reagent manufactured by Toray Dow Corning Silicone Co., Ltd., AX43-01) was used.
An airgel sample was obtained in the same manner as in Example 1 except that 3) was used. -Example 10-In Example 2, tetraethoxysilane (a reagent manufactured by Toray Dow Corning Silicone Co., Ltd.) was used instead of tetramethoxysilane, and the mixing ratio was tetraethoxysilane: ethanol: ammonia water = 1: 14 :. An airgel sample was obtained in the same manner as in Example 2 except that No. 12 was used.
【００３６】−実施例１１− 実施例１０において、０．０１mol/l のアンモニア水溶
液を用いる代わりに０．１mol/l の塩酸を用いたこと以
外は、実施例１０と同様にしてエアロゲル試料を得た。 −実施例１２− 実施例１において、テトラメトキシシランの代わりに３
官能アルコキシシランであるメチルトリメトキシシラン
を用いたこと以外は、実施例１と同様にしてエアロゲル
試料を得た。Example 11 An airgel sample was obtained in the same manner as in Example 10 except that 0.1 mol / l hydrochloric acid was used instead of 0.01 mol / l aqueous ammonia solution. It was -Example 12-In Example 1, it replaced with 3 instead of tetramethoxysilane.
An airgel sample was obtained in the same manner as in Example 1 except that methyltrimethoxysilane which was a functional alkoxysilane was used.
【００３７】−比較例１− 実施例１において、ゲル化物を熟成した後、疎水化処理
反応は行わずに、そのまま実施例１と同様の条件で超臨
界乾燥を行って、エアロゲル試料を得た。 −比較例２− 実施例３において、ゲル化物を熟成した後、疎水化処理
反応は行わずに、そのまま実施例３と同様の条件で超臨
界乾燥を行って、エアロゲル試料を得た。-Comparative Example 1-In Example 1, after aging the gelled product, without performing the hydrophobization reaction, supercritical drying was performed under the same conditions as in Example 1 to obtain an airgel sample. .. -Comparative Example 2-After aging the gelled product in Example 3, supercritical drying was performed as it was under the same conditions as in Example 3 without performing the hydrophobization reaction, to obtain an airgel sample.
【００３８】−比較例３− 実施例４において、ゲル化物を熟成した後、疎水化処理
反応は行わずに、そのまま実施例４と同様の条件で超臨
界乾燥を行って、エアロゲル試料を得た。 −比較例４− 実施例１において、ゲル化物を熟成した後、疎水化処理
反応は行わずに、そのまま常圧で８０〜１００℃に加熱
して乾燥を行って、ゲル乾燥物を得た。Comparative Example 3-After aging the gelled product in Example 4, supercritical drying was performed under the same conditions as in Example 4 without performing the hydrophobization reaction, and an airgel sample was obtained. .. -Comparative Example 4- In Example 1, after aging the gelled product, the hydrophobizing reaction was not performed, and the gelled product was dried by heating at 80 to 100 ° C under normal pressure as it was.
【００３９】−比較例５− 実施例２において、ゲル化物を熟成した後、ヘキサメチ
ルジシラザンを用いて疎水化処理反応を行ったものを、
そのまま常圧で８０〜１００℃に加熱して乾燥を行い、
ゲル乾燥物を得た。実施例１〜１２および比較例１〜５
で得られた試料の内容を表１および２に示した。Comparative Example 5 In Example 2, after aging the gelled product, a reaction for hydrophobizing treatment using hexamethyldisilazane was carried out.
As it is, it is heated to 80 to 100 ° C under normal pressure to dry it,
A gel dried product was obtained. Examples 1-12 and Comparative Examples 1-5
Tables 1 and 2 show the contents of the samples obtained in 1.
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【表２】 [Table 2]
【００４２】実施例１〜１２および比較例１〜５で得ら
れた試料について、かさ密度、比表面積、熱伝導率、光
透過率、および、湿気による経時劣化を調べた。比表面
積は窒素吸着法によるＢＥＴ法を利用して求めた。熱伝
導率は、英弘精機（株）製の定常法による熱伝導率測定
装置を使用して、ＡＳＴＭ−Ｃ５１８に準拠した方法
で、設定温度２０℃と４０℃の条件で測定した。The samples obtained in Examples 1 to 12 and Comparative Examples 1 to 5 were examined for bulk density, specific surface area, thermal conductivity, light transmittance, and deterioration with time due to moisture. The specific surface area was determined by using the BET method based on the nitrogen adsorption method. The thermal conductivity was measured at a set temperature of 20 ° C. and 40 ° C. by a method according to ASTM-C518 using a thermal conductivity measuring device by a steady method manufactured by Eiko Seiki Co., Ltd.
【００４３】光透過率は、試料の透過光について、可視
光域の分光分布を測定し、可視光透過率をＪＩＳ−Ｒ３
１０６に基づいて求めた。湿気による経時変化は、試料
を、温度６０℃、相対湿度９０％の恒温恒湿槽内に４８
時間放置し、その前後の試料の熱伝導率および光透過率
を測定した。結果を表３および４に示した。The light transmittance was measured by measuring the spectral distribution in the visible light region of the light transmitted through the sample, and the visible light transmittance was measured according to JIS-R3.
Based on 106. For the change over time due to humidity, place the sample in a constant temperature and humidity chamber at a temperature of 60 ° C and a relative humidity of 90%.
The sample was allowed to stand for a period of time, and the thermal conductivity and light transmittance of the sample before and after that were measured. The results are shown in Tables 3 and 4.
【００４４】なお、試料のかさ密度が大きいということ
は、乾燥前には同じ大きさの成形体だったのが、乾燥に
よる収縮が大きいということを示し、かさ密度が小さい
ということは、乾燥による収縮が小さいということを示
す。The large bulk density of the sample means that the molded article having the same size before drying has a large shrinkage due to drying, and the small bulk density means that the bulk density due to drying is large. Indicates that the contraction is small.
【００４５】[0045]
【表３】 [Table 3]
【００４６】[0046]
【表４】 [Table 4]
【００４７】表にみるように、実施例のエアロゲルは、
乾燥時の収縮が全く無く、そのために保持する多孔性が
優れているため、断熱性、光透過性に優れ、しかも、水
分等の吸着がなく、これらの経時変化がないものになっ
ている。これに比べ、比較例１〜３では、超臨界乾燥を
行っても乾燥時、微小ではあるが収縮を起こし、また、
水分等の吸着性が非常によいため、湿気によって著しく
性能が劣化する。また、比較例４，５では、乾燥時に著
しく収縮を起こしてしまい、断熱性能は悪いものとなっ
ている。なお、比較例と、これに対応する実施例とを対
比すると、かさ密度の数値に大小があるが、この差は、
乾燥時の収縮の大小により生じているものであり、疎水
化処理剤の有無による影響は小さかった。As shown in the table, the airgel of the example is
Since there is no shrinkage at the time of drying, and therefore, the retained porosity is excellent, the heat insulating property and the light transmitting property are excellent, and moreover, moisture and the like are not adsorbed, and these do not change with time. On the contrary, in Comparative Examples 1 to 3, even when supercritical drying is performed, a small amount of shrinkage occurs during drying,
Since it has a very good ability to adsorb moisture and the like, the performance is significantly degraded by moisture. Further, in Comparative Examples 4 and 5, shrinkage remarkably occurs during drying, and the heat insulation performance is poor. In addition, when comparing the comparative example and the corresponding example, there are large and small numerical values of the bulk density, but this difference is
It was caused by the degree of shrinkage during drying, and the influence of the presence or absence of the hydrophobizing agent was small.
【００４８】−実施例１３− ４官能アルコキシシランであるテトラメトキシシラン
（東レダウコーニングシリコーン（株）製試薬）に、エ
タノール（ナカライテスク（株）製特級試薬）と０．０
１mol/l のアンモニア水とを混合した混合液を徐々に添
加した。この際、混合比は、テトラメトキシシラン：エ
タノール：アンモニア水＝１：５：４（モル比）であ
り、２０℃に保って１時間攪拌しながら加水分解を進
め、直径５１mmの容器内で静置して、ゲル化させた。さ
らに、エタノールを加え、５０℃で加熱しながらエタノ
ールの添加を繰り返してゲルが乾燥しないように縮重合
反応を加速（熟成）することにより、直径が５１mmで厚
みが５mmの、（ＳｉＯ2)m を骨格に有するゲル状のポリ
マー〔アルコゲル〕を得た。Example 13 Tetramethoxysilane (reagent manufactured by Toray Dow Corning Silicone Co., Ltd.) which is a tetrafunctional alkoxysilane, ethanol (special grade reagent manufactured by Nacalai Tesque Co., Ltd.) and 0.0.
A mixed solution mixed with 1 mol / l ammonia water was gradually added. At this time, the mixing ratio was tetramethoxysilane: ethanol: ammonia water = 1: 5: 4 (molar ratio), the hydrolysis was promoted while maintaining the temperature at 20 ° C. for 1 hour with stirring, and the mixture was allowed to stand in a container having a diameter of 51 mm. It was placed and gelled. Furthermore, by adding ethanol and repeating the addition of ethanol while heating at 50 ° C. to accelerate (age) the polycondensation reaction so as not to dry the gel, (SiO 2 ) m with a diameter of 51 mm and a thickness of 5 mm is obtained. A gel-like polymer [alcogel] having a skeleton was obtained.
【００４９】このゲル状のポリマー〔アルコゲル〕を疎
水化処理するため、ヘキサメチルジシラザン（東レダウ
コーニングシリコーン（株）製試薬）を０．２mol/l の
割合でトルエンに溶解させてトルエン溶液を調製し、上
記のゲル状のポリマー〔アルコゲル〕をその容積に対し
て５倍量の上記トルエン溶液中に移し、２４時間かけて
ヘキサメチルジシラザンをポリマー内に浸透させた。そ
の後、１１０℃で２時間程度加熱しながら還流攪拌し
て、疎水化処理された変性ポリマーのゲルを得た。To hydrophobize the gel-like polymer [alcogel], hexamethyldisilazane (a reagent manufactured by Toray Dow Corning Silicone Co., Ltd.) was dissolved in toluene at a ratio of 0.2 mol / l to prepare a toluene solution. The gel-like polymer [alcogel] prepared above was transferred into the toluene solution in an amount 5 times the volume thereof, and hexamethyldisilazane was permeated into the polymer for 24 hours. Then, the mixture was refluxed and stirred at 110 ° C. for about 2 hours to obtain a hydrophobized modified polymer gel.
【００５０】この変性ポリマー〔ゲル〕をエタノール中
に移し、２４時間かけてエタノールによる溶媒の交換を
繰り返し、未反応のヘキサメチルジシラザンとトルエン
を除去して、エタノールに溶媒を置換した。次に、この
ゲル〔アルコゲル〕を１８℃、５５気圧の液化二酸化炭
素中に入れ、アルコゲル内のエタノールを二酸化炭素に
置換する操作を３時間行った。その後、ゲルをオートク
レーブ内に移し、さらにこのオートクレーブ内をエタノ
ールと二酸化炭素の混合分散媒で満たし、この混合分散
媒の超臨界条件である８０℃、１６０気圧にし、超臨界
乾燥を約４８時間行って、エアロゲル試料を得た。この
試料の性状は、微細な多孔質で、透明で、かつ、軽量な
ものであった。This modified polymer [gel] was transferred into ethanol, and the solvent exchange with ethanol was repeated for 24 hours to remove unreacted hexamethyldisilazane and toluene, and the solvent was replaced with ethanol. Next, this gel [alcogel] was placed in liquefied carbon dioxide at 18 ° C. and 55 atm, and the operation of replacing ethanol in the alcogel with carbon dioxide was performed for 3 hours. After that, the gel is transferred into an autoclave, and the inside of the autoclave is filled with a mixed dispersion medium of ethanol and carbon dioxide, and the mixed dispersion medium is subjected to supercritical conditions of 80 ° C. and 160 atm, and supercritical drying is performed for about 48 hours. To obtain an airgel sample. The properties of this sample were fine, porous, transparent, and lightweight.
【００５１】−実施例１４− 実施例１３において、ヘキサメチルジシラザンを用いる
代わりにトリメチルクロロシランを用いたこと以外は実
施例１３と同様にして、エアロゲル試料を得た。 −実施例１５− 実施例１３と同様にして得られた変性ポリマー〔ゲル〕
をエタノール中に移し、２４時間エタノールによる溶媒
の交換を繰り返し、未反応のヘキサメチルジシラザンと
トルエンを除去して、エタノールに溶媒を置換したゲル
〔アルコゲル〕を得た。Example 14 An airgel sample was obtained in the same manner as in Example 13 except that trimethylchlorosilane was used instead of using hexamethyldisilazane. -Example 15-Modified polymer obtained in the same manner as in Example 13 [gel]
Was transferred to ethanol, and the solvent exchange with ethanol was repeated for 24 hours to remove unreacted hexamethyldisilazane and toluene to obtain a gel [alcogel] in which the solvent was replaced with ethanol.
【００５２】次に、このゲル〔アルコゲル〕をオートク
レーブ内に移し、さらにこのオートクレーブ内をエタノ
ールからなる分散媒で満たし、エタノールの超臨界条件
である２５０℃、８０気圧にし、超臨界乾燥を約６時間
行って、エアロゲル試料を得た。 −実施例１６− テトラエトキシシランに、エタノールと０．０１mol/l
のアンモニア水とを混合した混合液を徐々に添加した。
この際、混合比は、テトラエトキシシラン：エタノー
ル：アンモニア水＝１：５．５：５（モル比）であり、
２０℃に保って１時間攪拌しながら加水分解を進め、実
施例１３と同様の容器内で静置して、ゲル化させた。さ
らに、エタノールを加え、５０℃で加熱しながらエタノ
ールの添加を繰り返してゲルが乾燥しないように縮重合
反応を加速（熟成）することにより、（ＳｉＯ2)m を骨
格に有するゲル状のポリマー〔アルコゲル〕を得た。Next, this gel [alcogel] was transferred into an autoclave, and the inside of the autoclave was filled with a dispersion medium composed of ethanol, and the ethanol was brought to a supercritical condition of 250 ° C. and 80 atm, and supercritical drying was performed at about 6 times. Airgel samples were obtained over time. -Example 16-Ethanol and 0.01 mol / l were added to tetraethoxysilane.
A mixed solution obtained by mixing with ammonia water was gradually added.
At this time, the mixing ratio was tetraethoxysilane: ethanol: ammonia water = 1: 5.5: 5 (molar ratio),
Hydrolysis proceeded while maintaining the temperature at 20 ° C. for 1 hour with stirring, and allowed to stand in the same container as in Example 13 to cause gelation. Furthermore, by adding ethanol and repeating heating while heating at 50 ° C. to accelerate (age) the polycondensation reaction so as not to dry the gel, a gel-like polymer [SiO 2 ] m in the skeleton [ Alcogel] was obtained.
【００５３】このポリマー〔アルコゲル〕を用い、後は
実施例１３と同様の操作を行って、エアロゲル試料を得
た。 −実施例１７− テトラエトキシシランに、エタノールと０．０４mol/l
のフッ化アンモニウム水溶液とを混合した混合液を徐々
に添加した。この際、混合比は、テトラエトキシシラ
ン：エタノール：フッ化アンモニウム水溶液＝１：５．
５：５（モル比）であり、２０℃に保って１時間攪拌し
ながら加水分解を進め、実施例１３と同様の容器内で静
置して、ゲル化させた。さらに、エタノールを加え、５
０℃で加熱しながらエタノールの添加を繰り返してゲル
が乾燥しないように縮重合反応を加速（熟成）すること
により、（ＳｉＯ2)m を骨格に有するゲル状のポリマー
〔アルコゲル〕を得た。Using this polymer [alcogel], the same procedure as in Example 13 was carried out to obtain an airgel sample. Example 17 Tetraethoxysilane, ethanol and 0.04 mol / l
The mixed solution obtained by mixing with the ammonium fluoride aqueous solution of was gradually added. At this time, the mixing ratio is tetraethoxysilane: ethanol: ammonium fluoride aqueous solution = 1: 5.
It was 5: 5 (molar ratio), and hydrolysis was promoted while maintaining it at 20 ° C. for 1 hour with stirring, and allowed to stand in the same container as in Example 13 to cause gelation. Add ethanol and add 5
By repeating the addition of ethanol while heating at 0 ° C. to accelerate (age) the polycondensation reaction so as not to dry the gel, a gel polymer (alcogel) having (SiO 2 ) m in the skeleton was obtained.
【００５４】このポリマー〔アルコゲル〕を用い、後は
実施例１３と同様の操作を行って、エアロゲル試料を得
た。 −実施例１８− 実施例１３と同様にして得られた変性ポリマー〔ゲル〕
をエタノール中に移し、２４時間エタノールによる溶媒
の交換を繰り返し、未反応のヘキサメチルジシラザンと
トルエンを除去して、エタノールに溶媒を置換したゲル
〔アルコゲル〕を得た。Using this polymer [alcogel], the same procedure as in Example 13 was carried out to obtain an airgel sample. -Example 18- Modified polymer [gel] obtained in the same manner as in Example 13
Was transferred to ethanol, and the solvent exchange with ethanol was repeated for 24 hours to remove unreacted hexamethyldisilazane and toluene to obtain a gel [alcogel] in which the solvent was replaced with ethanol.
【００５５】次に、このゲル〔アルコゲル〕を１８℃、
５５気圧の液化二酸化炭素中に入れ、アルコゲル中のエ
タノールを二酸化炭素に完全に置換した。その後、オー
トクレーブ内に移し、さらにこのオートクレーブ内を二
酸化炭素で満たし、二酸化炭素の超臨界条件である４０
℃、８０気圧にし、超臨界乾燥を約２４時間行って、エ
アロゲル試料を得た。Next, this gel [alcogel] was treated at 18 ° C.
It was placed in liquefied carbon dioxide at 55 atm, and the ethanol in the alcogel was completely replaced with carbon dioxide. After that, the autoclave is moved into the autoclave, and the inside of the autoclave is filled with carbon dioxide.
The temperature was adjusted to 80 atm and supercritical drying was performed for about 24 hours to obtain an airgel sample.
【００５６】−実施例１９− ２官能アルコキシシランであるジメチルジメトキシシラ
ンと４官能のテトラメトキシシランとをモル比で１：９
の割合で含む混合物に、エタノールと０．０１mol/l の
アンモニウム水とを混合した混合液を徐々に添加した。
この際、混合比は、テトラメトキシシラン：エタノー
ル：アンモニウア水＝１：５：４（モル比）であり、２
０℃に保って１時間攪拌しながら加水分解を進め、実施
例１３と同様の容器内で静置して、ゲル化させた。さら
に、エタノールを加え、５０℃で加熱しながらエタノー
ルの添加を繰り返してゲルが乾燥しないように縮重合反
応を加速（熟成）することにより、（ＳｉＯ2)m を骨格
に有するゲル状のポリマー〔アルコゲル〕を得た。Example 19 Bifunctional alkoxysilane dimethyldimethoxysilane and tetrafunctional tetramethoxysilane in a molar ratio of 1: 9.
A mixture of ethanol and 0.01 mol / l ammonium water was gradually added to the mixture containing the above mixture.
At this time, the mixing ratio was tetramethoxysilane: ethanol: ammonium water = 1: 5: 4 (molar ratio), and 2
The hydrolysis was allowed to proceed with stirring at 0 ° C. for 1 hour, and the mixture was allowed to stand in the same container as in Example 13 to cause gelation. Furthermore, by adding ethanol and repeating heating while heating at 50 ° C. to accelerate (age) the polycondensation reaction so as not to dry the gel, a gel-like polymer [SiO 2 ] m in the skeleton [ Alcogel] was obtained.
【００５７】このポリマー〔アルコゲル〕を用い、後は
実施例１３と同様の操作を行って、エアロゲル試料を得
た。 −実施例２０− ３官能アルコキシシランであるメチルトリメトキシシラ
ンと４官能のテトラメトキシシランとをモル比で５：５
の割合で含む混合物に、エタノールと０．０１mol/l の
アンモニウム水とを混合した混合液を徐々に添加した。
この際、混合比は、テトラメトキシシラン：エタノー
ル：アンモニウア水＝１：５：４（モル比）であり、２
０℃に保って１時間攪拌しながら加水分解を進め、実施
例１３と同様の容器内で静置して、ゲル化させた。さら
に、エタノールを加え、５０℃で加熱しながらエタノー
ルの添加を繰り返してゲルが乾燥しないように縮重合反
応を加速（熟成）することにより、（ＳｉＯ2)m を骨格
に有するゲル状のポリマー〔アルコゲル〕を得た。Using this polymer [alcogel], the same procedure as in Example 13 was carried out to obtain an airgel sample. -Example 20- Methyltrimethoxysilane, which is a trifunctional alkoxysilane, and tetrafunctional silane, which is tetrafunctional, are in a molar ratio of 5: 5.
A mixture of ethanol and 0.01 mol / l ammonium water was gradually added to the mixture containing the above mixture.
At this time, the mixing ratio was tetramethoxysilane: ethanol: ammonium water = 1: 5: 4 (molar ratio), and 2
The hydrolysis was allowed to proceed with stirring at 0 ° C. for 1 hour, and the mixture was allowed to stand in the same container as in Example 13 to cause gelation. Furthermore, by adding ethanol and repeating heating while heating at 50 ° C. to accelerate (age) the polycondensation reaction so as not to dry the gel, a gel-like polymer [SiO 2 ] m in the skeleton [ Alcogel] was obtained.
【００５８】このポリマー〔アルコゲル〕を用い、後は
実施例１３と同様の操作を行って、エアロゲル試料を得
た。 −実施例２１− 実施例１３と同様にして得られた（ＳｉＯ2)m を骨格に
有するゲル状のポリマー〔アルコゲル〕を、疎水化処理
剤として無水酢酸および触媒としてピリジン１０ccを含
むトルエン溶液中に移し、２４時間かけて無水酢酸をポ
リマー内に浸透させた。その後、１１０℃で２時間程度
加熱しながら還流攪拌し、湿潤状態の疎水化された変性
ポリマー〔ゲル〕を得た。Using this polymer [alcogel], the same procedure as in Example 13 was carried out to obtain an airgel sample. - obtained in the same manner as Example 21 Example 13 (SiO 2) a gel-like polymer [alcogel] having a skeleton m, toluene solution containing pyridine 10cc as acetic anhydride and a catalyst as hydrophobizing agent And the acetic anhydride was permeated into the polymer for 24 hours. Then, the mixture was refluxed with stirring at 110 ° C. for about 2 hours to obtain a hydrophobic modified polymer [gel] in a wet state.
【００５９】この変性ポリマー〔ゲル〕を用い、後は実
施例１３と同様の操作を行って、エアロゲル試料を得
た。 −実施例２２− 実施例１３と同様にして（ＳｉＯ2)m を骨格に有するゲ
ル状のポリマー〔アルコゲル〕を調製した。これとは別
に、疎水化処理剤であるヘキサメチルジシラザンを０．
２mol/l の割合でエタノールに溶解させてエタノール溶
液を調製し、上記のゲル状のポリマー〔アルコゲル〕を
その容積に対して５倍量の上記エタノール溶液中に移
し、２４時間かけてヘキサメチルジシラザンをポリマー
内に浸透させた。その後、７０℃で２時間程度加熱しな
がら還流攪拌し、湿潤状態の疎水化された変性ポリマー
〔アルコゲル〕を得た。Using this modified polymer [gel], the same procedure as in Example 13 was carried out to obtain an airgel sample. -Example 22- In the same manner as in Example 13, a gel-like polymer [alcogel] having (SiO 2 ) m in its skeleton was prepared. Separately, the hydrophobizing agent hexamethyldisilazane was added to 0.1.
An ethanol solution was prepared by dissolving it in ethanol at a ratio of 2 mol / l, and the above gel-like polymer [alcogel] was transferred into the ethanol solution in an amount 5 times the volume of the above solution, and hexamethyldiethyl was taken over 24 hours. The silazane was infiltrated into the polymer. Then, the mixture was refluxed with stirring at 70 ° C. for about 2 hours to obtain a hydrophobic modified polymer [alcogel] in a wet state.
【００６０】この変性ポリマー〔アルコゲル〕を用い、
後は実施例１３と同様の操作を行って、エアロゲル試料
を得た。 −比較例６− 実施例１３と同様にして得られた（ＳｉＯ2)m を骨格に
有するゲル状のポリマー〔アルコゲル〕を疎水化処理剤
と反応させずにエタノール中に移し、２４時間かけてエ
タノールによる溶媒交換を繰り返して洗浄し、このアル
コゲルを１８℃、５５気圧の二酸化炭素中に入れ、アル
コゲル中のエタノールを二酸化炭素に置換する操作を３
時間行った。その後、ゲルをオートクレーブに移し、オ
ートクレーブ内をエタノールと二酸化炭素の混合分散媒
で満たし、この混合分散媒の超臨界条件である８０℃、
１６０気圧にし、超臨界乾燥を約４８時間行って、エア
ロゲル試料を得た。このエアロゲル試料の性状は、微細
な多孔質で、透明かつ軽量なものであったが、より寸法
が小さく、かさ密度は大きなものになっていた。Using this modified polymer [alcogel],
After that, the same operation as in Example 13 was performed to obtain an airgel sample. —Comparative Example 6— A gel polymer (alcogel) having (SiO 2 ) m in the skeleton obtained in the same manner as in Example 13 was transferred into ethanol without reacting with the hydrophobizing agent, and the reaction was continued for 24 hours. The solvent is repeatedly exchanged with ethanol for washing, and this alcogel is placed in carbon dioxide at 18 ° C. and 55 atm to replace ethanol in the alcogel with carbon dioxide.
Went on time. After that, the gel is transferred to an autoclave, the interior of the autoclave is filled with a mixed dispersion medium of ethanol and carbon dioxide, and the supercritical condition of this mixed dispersion medium is 80 ° C.,
Air pressure was adjusted to 160 atm and supercritical drying was performed for about 48 hours to obtain an airgel sample. The properties of this airgel sample were fine porous, transparent and lightweight, but the size was smaller and the bulk density was larger.
【００６１】−比較例７− 実施例１３と同様にして得られた（ＳｉＯ2)m を骨格に
有するゲル状のポリマー〔アルコゲル〕を疎水化処理剤
と反応させずにエタノール中に移し、２４時間かけてエ
タノールによる溶媒交換を繰り返して洗浄し、このアル
コゲルをオートクレーブに移し、オートクレーブ内をエ
タノールからなる分散媒で満たし、エタノールの超臨界
条件である２５０℃、８０気圧にし、超臨界乾燥を約６
時間行って、エアロゲル試料を得た。Comparative Example 7 A gel polymer (alcogel) having (SiO 2 ) m in the skeleton obtained in the same manner as in Example 13 was transferred into ethanol without reacting with the hydrophobizing agent, and 24 The solvent was repeatedly exchanged with ethanol for a long time to wash, the alcogel was transferred to an autoclave, and the interior of the autoclave was filled with a dispersion medium composed of ethanol. 6
Airgel samples were obtained over time.
【００６２】−比較例８− 実施例１６と同様にして得られた（ＳｉＯ2)m を骨格に
有するゲル状のポリマー〔アルコゲル〕を疎水化処理剤
と反応させずにエタノール中に移し、２４時間かけてエ
タノールによる溶媒交換を繰り返して洗浄し、この後は
実施例１６と同様の操作を行って、エアロゲル試料を得
た。Comparative Example 8 The gel-like polymer (alcogel) having (SiO 2 ) m in the skeleton obtained in the same manner as in Example 16 was transferred into ethanol without reacting with the hydrophobizing agent, and 24 The solvent exchange with ethanol was repeated over time for washing, and thereafter, the same operation as in Example 16 was performed to obtain an airgel sample.
【００６３】−比較例９− 実施例１３と同様にして得られた（ＳｉＯ2)m を骨格に
有するゲル状のポリマー〔アルコゲル〕を、疎水化処理
剤と反応させずにそのまま２０℃、常圧（１気圧）下で
１週間大気乾燥して、キセロゲル試料を得た。このキセ
ロゲル試料は、多孔質の度合が低いものであった。-Comparative Example 9- A gel polymer (alcogel) having (SiO 2 ) m in the skeleton obtained in the same manner as in Example 13 was allowed to stand at 20 ° C. as it was without reacting with the hydrophobizing agent. A xerogel sample was obtained by air-drying for 1 week under pressure (1 atm). This xerogel sample had a low degree of porosity.
【００６４】−比較例１０− 実施例１３と同様にして疎水化処理して得られたゲル状
の変性ポリマーを、２０℃、常圧（１気圧）下で１週間
大気乾燥して、キセロゲル試料を得た。このキセロゲル
試料は、多孔質の度合が低いものであった。実施例１３
〜２２および比較例６〜１０で得られた試料の内容を表
５および６に示した。Comparative Example 10 A gel-like modified polymer obtained by hydrophobizing in the same manner as in Example 13 was air-dried at 20 ° C. under normal pressure (1 atm) for 1 week to give a xerogel sample. Got This xerogel sample had a low degree of porosity. Example 13
Tables 5 and 6 show the contents of the samples obtained in Examples 22 to 22 and Comparative Examples 6 to 10.
【００６５】[0065]
【表５】 [Table 5]
【００６６】[0066]
【表６】 [Table 6]
【００６７】実施例１３〜２２および比較例６〜１０で
得られた試料について、比表面積、かさ密度、熱伝導
率、光透過率、および、耐湿性（湿気による経時劣化）
を調べた。比表面積、かさ密度、熱伝導率および光透過
率は、前記と同様にして測定した。耐湿性（湿気による
経時劣化）は、試料を、温度６０℃、相対湿度９０％の
恒温恒湿槽内に４８時間放置して、試料に湿気を付与
し、その前後の試料のかさ密度、熱伝導率および光透過
率を測定することにより調べた。With respect to the samples obtained in Examples 13 to 22 and Comparative Examples 6 to 10, specific surface area, bulk density, thermal conductivity, light transmittance, and humidity resistance (deterioration due to humidity over time).
I checked. The specific surface area, bulk density, thermal conductivity and light transmittance were measured in the same manner as above. Moisture resistance (deterioration due to humidity over time) is measured by leaving the sample in a constant temperature and humidity chamber at a temperature of 60 ° C. and a relative humidity of 90% for 48 hours to apply moisture to the sample, and to measure the bulk density and heat of the sample before and after that. It was investigated by measuring conductivity and light transmittance.
【００６８】それらの結果を表７および８に示した。The results are shown in Tables 7 and 8.
【００６９】[0069]
【表７】 [Table 7]
【００７０】[0070]
【表８】 [Table 8]
【００７１】表７および８にみるように、実施例１３〜
２２で得られた試料は、比較例６〜１０で得られた試料
に比べてかさ密度が小さくなっている。実施例１３〜２
２では、ゲルを疎水化処理した後、超臨界乾燥している
ため、溶媒除去による収縮を起こしておらず、比較例６
〜８では、疎水化処理を施していないため、超臨界乾燥
しても幾分かの収縮を起こしており、また、比較例９〜
１０では、ゲルを通常の方法で乾燥しているため、疎水
化処理の有無に関わらず、大きな収縮を起こしているこ
とが確認された。As seen in Tables 7 and 8, Examples 13-
The bulk density of the sample obtained in No. 22 is smaller than that of the samples obtained in Comparative Examples 6 to 10. Examples 13-2
In No. 2, since the gel was hydrophobized and then supercritically dried, no shrinkage was caused by solvent removal.
In Nos. 8 to 8, since no hydrophobizing treatment was performed, some shrinkage occurred even after supercritical drying, and Comparative Examples 9 to
In No. 10, since the gel was dried by a usual method, it was confirmed that a large shrinkage occurred regardless of the presence or absence of the hydrophobic treatment.
【００７２】実施例１３および比較例６で得られた試料
について、超臨界乾燥前、超臨界乾燥直後および上記の
耐湿試験後におけるかさ密度および可視光透過率を求め
た結果をそれぞれ図１および２のグラフにプロットし、
その変化を示した。これらの図中、実施例１３のものは
「●」で、比較例６のものは「○」でプロットした。な
お、超臨界乾燥前におけるかさ密度とは、ゲルの固相で
ある二酸化ケイ素の重量をゲル全体の体積で割ったもの
である。With respect to the samples obtained in Example 13 and Comparative Example 6, the bulk density and the visible light transmittance were determined before supercritical drying, immediately after supercritical drying and after the above moisture resistance test. The results are shown in FIGS. 1 and 2, respectively. Plot on the graph of
The change was shown. In these figures, those of Example 13 are plotted with “●”, and those of Comparative Example 6 are plotted with “◯”. The bulk density before supercritical drying is the weight of silicon dioxide, which is the solid phase of the gel, divided by the volume of the entire gel.
【００７３】図１および２にみるように、疎水化処理を
施した後に超臨界乾燥を行って得られた実施例１３のエ
アロゲルは、疎水化処理を施さずに超臨界乾燥を行って
得られた比較例６のエアロゲルに比べて、初期の特性が
長く維持されており、水と接触しても特性の劣化が見ら
れない優れた耐水性を有するものであることが確認され
た。As shown in FIGS. 1 and 2, the airgel of Example 13 obtained by performing supercritical drying after subjecting it to hydrophobic treatment was obtained by performing supercritical drying without subjecting it to hydrophobic treatment. It was confirmed that, compared with the airgel of Comparative Example 6, the initial properties were maintained for a longer period of time and the water resistance was excellent with no deterioration in properties even when contacted with water.
【００７４】[0074]
【発明の効果】この発明の疎水性エアロゲルの製造方法
によれば、湿潤ゲルの乾燥時に多孔体構造が収縮するこ
とがなく、断熱性等、多孔質材料に特有の機能や光透過
性に優れ、しかも、水分等の吸着による上記性能の経時
劣化がないエアロゲル体を得ることができる。EFFECTS OF THE INVENTION According to the method for producing a hydrophobic airgel of the present invention, the porous structure does not shrink when the wet gel is dried, and the heat-insulating property and other functions peculiar to the porous material and the light transmittance are excellent. Moreover, it is possible to obtain an airgel body that does not deteriorate with time due to adsorption of water and the like.
【００７５】この製造方法によって得られた疎水性エア
ロゲルは、上記の優れた性能を有するものであるため、
特に断熱材、さらには音響材料等の様々な用途に有用で
あり、プレート状、粉状等、色々な形態で利用すること
ができる。また、チェレンコフ素子等の用途にも用いる
ことができる。Since the hydrophobic airgel obtained by this production method has the above-mentioned excellent performance,
In particular, it is useful for various applications such as a heat insulating material and further an acoustic material, and can be used in various forms such as a plate shape and a powder shape. It can also be used for applications such as Cherenkov elements.
【図１】実施例１３および比較例６で得られたエアロゲ
ル試料について、超臨界乾燥前、超臨界乾燥直後および
耐湿試験後におけるかさ密度を調べた結果を、実施例１
３のものは「●」で、比較例６のものは「○」でプロッ
トして示したグラフである。FIG. 1 shows the results of examining the bulk densities of airgel samples obtained in Example 13 and Comparative Example 6 before supercritical drying, immediately after supercritical drying, and after a moisture resistance test.
3 is a graph plotted with "●", and that of Comparative Example 6 is plotted with "○".
【図２】実施例１３および比較例６で得られたエアロゲ
ル試料について、超臨界乾燥前、超臨界乾燥直後および
耐湿試験後における可視光透過率を調べた結果を、実施
例１３のものは「●」で、比較例６のものは「○」でプ
ロットして示したグラフである。FIG. 2 shows the results of examining the visible light transmittance of the airgel samples obtained in Example 13 and Comparative Example 6 before supercritical drying, immediately after supercritical drying, and after a moisture resistance test. In the graph, “●” indicates that in Comparative Example 6 is plotted by “◯”.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 上垣百合子 大阪府門真市大字門真1048番地松下電工株 式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuriko Uegaki 1048, Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Works Co., Ltd.
Claims (16)
で、かつ、シラノール基を有するポリマーを、前記シラ
ノール基に対して反応可能な官能基と疎水基を併せ持つ
疎水化処理剤と反応させて疎水化処理することにより得
られた変性ポリマーのゲルを超臨界乾燥させて疎水性エ
アロゲルを得るようにする疎水性エアロゲルの製造方
法。1. The skeleton has (SiO 2 ) m (m is a positive integer)
And a polymer having a silanol group is treated with a hydrophobizing agent having both a functional group capable of reacting with the silanol group and a hydrophobic group to hydrophobize the gel of the modified polymer, A method for producing a hydrophobic airgel, which comprises performing critical drying to obtain a hydrophobic airgel.
が、ハロゲン、アミノ基、イミノ基、カルボキシル基お
よびアルコキシル基からなる群の中から選ばれた少なく
とも１種である請求項１記載の疎水性エアロゲルの製造
方法。2. The hydrophobic group according to claim 1, wherein the functional group capable of reacting with the silanol group is at least one selected from the group consisting of halogen, amino group, imino group, carboxyl group and alkoxyl group. Of manufacturing aerogels.
びそれらのフッ化物からなる群の中から選ばれた少なく
とも１種である請求項１または２記載の疎水性エアロゲ
ルの製造方法。3. The method for producing a hydrophobic aerogel according to claim 1, wherein the hydrophobic group is at least one selected from the group consisting of an alkyl group, a phenyl group and a fluoride thereof.
項１から３までのいずれかに記載の疎水性エアロゲルの
製造方法。4. The method for producing a hydrophobic airgel according to claim 1, wherein the hydrophobizing agent is a silane compound.
ン、ヘキサメチルジシロキサン、トリメチルクロロシラ
ン、トリメチルメトキシシラン、トリメチルエトキシシ
ラン、トリエチルエトキシシラン、トリエチルメトキシ
シラン、ジメチルジクロロシラン、ジメチルジエトキシ
シラン、ジエチルジエトキシシラン、メチルトリクロロ
シランおよびエチルトリクロロシランからなる群の中か
ら選ばれた少なくとも１種である請求項４記載の疎水性
エアロゲルの製造方法。5. The silane compound is hexamethyldisilazane, hexamethyldisiloxane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triethylmethoxysilane, dimethyldichlorosilane, dimethyldiethoxysilane, diethyldiethoxy. The method for producing a hydrophobic airgel according to claim 4, which is at least one selected from the group consisting of silane, methyltrichlorosilane and ethyltrichlorosilane.
ゲン化アルキルからなる群の中から選ばれた少なくとも
１種である請求項２または３記載の疎水性エアロゲルの
製造方法。6. The method for producing a hydrophobic airgel according to claim 2, wherein the hydrophobizing agent is at least one selected from the group consisting of carboxylic acids and alkyl halides.
際、前記ゲルに含まれる分散媒を、この分散媒よりも臨
界点の低い化合物からなる分散媒に予め置換しておく請
求項１から６までのいずれかに記載の疎水性エアロゲル
の製造方法。7. When the gel of the modified polymer is subjected to supercritical drying, the dispersion medium contained in the gel is preliminarily replaced with a dispersion medium composed of a compound having a lower critical point than the dispersion medium. 6. The method for producing a hydrophobic airgel according to any one of 6 to 6.
請求項７記載の疎水性エアロゲルの製造方法。8. The method for producing a hydrophobic airgel according to claim 7, wherein the compound having a low critical point is carbon dioxide.
ル基を有するポリマーが、下記一般式（Ｉ）で表される
アルコキシシランを加水分解し、縮重合して得られたも
のである請求項１から８までのいずれかに記載の疎水性
エアロゲルの製造方法。 ＳｉＲ1 n （ＯＲ2)4-n …（Ｉ） 〔式中、Ｒ1 およびＲ2 は、互いに独立に、炭素数１〜
５のアルキル基またはフェニル基を表し、ｎは０〜２の
整数である。Ｒ1 およびＲ2 がそれぞれ２個以上ある場
合、２個以上のＲ1 、２個以上のＲ2 は、それぞれ、互
いに同じであってもよく、異なっていてもよい。〕9. A polymer having a skeleton of (SiO 2 ) m and having a silanol group is obtained by subjecting an alkoxysilane represented by the following general formula (I) to hydrolysis and polycondensation. A method for producing the hydrophobic airgel according to any one of claims 1 to 8. SiR 1 n (OR 2 ) 4-n (I) [In the formula, R 1 and R 2 are independently of each other, having 1 to 1 carbon atoms.
5 represents an alkyl group or a phenyl group, and n is an integer of 0-2. When each of R 1 and R 2 is 2 or more, 2 or more R 1 and 2 or more R 2 may be the same or different from each other. ]
ール基を有するポリマーが、前記一般式（Ｉ）で表され
るアルコキシシランを、水との相溶性を有し、かつ、ア
ルコキシシランを溶解する溶媒と、水との混合液を用い
て加水分解し、縮重合して得られたものである請求項９
記載の疎水性エアロゲルの製造方法。10. A polymer having a skeleton of (SiO 2 ) m and having a silanol group has compatibility with the alkoxysilane represented by the general formula (I) with water, and an alkoxysilane. 10. The compound is obtained by hydrolyzing and polycondensing a mixed solution of a solvent in which water is dissolved and water.
A method for producing the hydrophobic aerogel described.
シシランを溶解する溶媒が、メタノール、エタノール、
プロパノール、イソプロパノール、ブタノール、アセト
ンおよびＮ，Ｎ−ジメチルホルムアミドからなる群の中
から選ばれた少なくとも１種である請求項１０記載の疎
水性エアロゲルの製造方法。11. A solvent having compatibility with water and capable of dissolving an alkoxysilane is methanol, ethanol,
The method for producing a hydrophobic airgel according to claim 10, which is at least one selected from the group consisting of propanol, isopropanol, butanol, acetone and N, N-dimethylformamide.
を行う際に用いられる溶媒と同一種類の化合物を超臨界
乾燥の媒体として用いる請求項１０または１１記載の疎
水性エアロゲルの製造方法。12. The method for producing a hydrophobic airgel according to claim 10, wherein a compound of the same type as the solvent used for the hydrolysis and polycondensation of the alkoxysilane is used as a medium for supercritical drying.
シシランをアルコールと水の存在下で加水分解し、縮重
合して得られた、骨格が（ＳｉＯ2)m で、かつ、シラノ
ール基を有するポリマーのアルコゲルを、疎水化処理剤
に対する溶解性が前記アルコールよりも高い溶媒で前記
疎水化処理剤を溶解させた処理液で疎水化処理して、変
性ポリマーのゲルを得、このゲル中の溶媒をアルコール
に置換し、次いで、この溶媒置換された変性ポリマーの
ゲル中のアルコールの全部または一部をアルコールより
も臨界点の低い二酸化炭素に置換した後、二酸化炭素の
単独系または二酸化炭素とアルコールとの混合系の臨界
点以上の温度圧力下で超臨界乾燥することにより疎水性
エアロゲルを得る請求項１０記載の疎水性エアロゲルの
製造方法。13. An alkoxysilane represented by the general formula (I) is hydrolyzed in the presence of alcohol and water and polycondensed to obtain a skeleton having (SiO 2 ) m and a silanol group. The polymer alcogel having a hydrophobizing agent is subjected to a hydrophobizing treatment with a treatment liquid in which the hydrophobizing agent is dissolved in a solvent having a higher solubility for the hydrophobizing agent than the alcohol to obtain a gel of a modified polymer. The solvent is replaced with alcohol, and then all or part of the alcohol in the solvent-substituted gel of the modified polymer is replaced with carbon dioxide having a lower critical point than alcohol, and then a single system of carbon dioxide or carbon dioxide is used. The method for producing a hydrophobic aerogel according to claim 10, wherein the hydrophobic aerogel is obtained by supercritical drying under a temperature and pressure equal to or higher than a critical point of a mixed system of alkanol and alcohol.
シシランをアルコールと水の存在下で加水分解し、縮重
合して得られた、骨格が（ＳｉＯ2)m で、かつ、シラノ
ール基を有するポリマーのアルコゲルを、疎水化処理剤
に対する溶解性が前記アルコールよりも高い溶媒で前記
疎水化処理剤を溶解させた処理液で疎水化処理して、変
性ポリマーのゲルを得、このゲル中の溶媒をアルコール
に置換した後、このアルコールの臨界点以上の温度圧力
下で超臨界乾燥することにより疎水性エアロゲルを得る
請求項１０記載の疎水性エアロゲルの製造方法。14. An alkoxysilane represented by the general formula (I) is hydrolyzed in the presence of alcohol and water and polycondensed to obtain a skeleton having (SiO 2 ) m and a silanol group. The polymer alcogel having a hydrophobizing agent is subjected to a hydrophobizing treatment with a treatment liquid in which the hydrophobizing agent is dissolved in a solvent having a higher solubility for the hydrophobizing agent than the alcohol to obtain a gel of a modified polymer. 11. The method for producing a hydrophobic aerogel according to claim 10, wherein the hydrophobic aerogel is obtained by substituting the solvent with alcohol and then supercritically drying at a temperature and pressure not lower than the critical point of the alcohol.
媒が、アルコールよりも高い沸点を有するものである請
求項１３または１４記載の疎水性エアロゲルの製造方
法。15. The method for producing a hydrophobic airgel according to claim 13 or 14, wherein the solvent of the treatment liquid in which the hydrophobizing treatment agent is dissolved has a boiling point higher than that of alcohol.
媒がトルエンである請求項１５記載の疎水性エアロゲル
の製造方法。16. The method for producing a hydrophobic airgel according to claim 15, wherein the solvent of the treatment liquid in which the hydrophobic treatment agent is dissolved is toluene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1794292 | 1992-02-03 | ||
| JP4-17942 | 1992-02-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05279011A true JPH05279011A (en) | 1993-10-26 |
| JP2659155B2 JP2659155B2 (en) | 1997-09-30 |
Family
ID=11957836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25508592A Expired - Lifetime JP2659155B2 (en) | 1992-02-03 | 1992-09-24 | Method for producing hydrophobic airgel |
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| Country | Link |
|---|---|
| JP (1) | JP2659155B2 (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0585456A4 (en) * | 1992-02-18 | 1994-08-17 | Matsushita Electric Works Ltd | Process for producing hydrophobic aerogel |
| EP0653377A1 (en) * | 1993-11-12 | 1995-05-17 | Matsushita Electric Works, Ltd. | Process of forming a hydrophobic aerogel |
| JPH07267756A (en) * | 1994-03-18 | 1995-10-17 | Basf Ag | Molding containing silica aerosol particle |
| WO1997010178A1 (en) * | 1995-09-13 | 1997-03-20 | Hoechst Research & Technology | Organofunctionalised aerogels |
| EP0849220A1 (en) * | 1996-12-20 | 1998-06-24 | Matsushita Electric Works, Ltd. | Process for producing aerogel |
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