WO2024038900A1 - Silica sol containing silicone compound, and resin composition - Google Patents
Silica sol containing silicone compound, and resin composition Download PDFInfo
- Publication number
- WO2024038900A1 WO2024038900A1 PCT/JP2023/029749 JP2023029749W WO2024038900A1 WO 2024038900 A1 WO2024038900 A1 WO 2024038900A1 JP 2023029749 W JP2023029749 W JP 2023029749W WO 2024038900 A1 WO2024038900 A1 WO 2024038900A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- silicone compound
- silica sol
- formula
- organic solvent
- Prior art date
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 209
- 150000001875 compounds Chemical class 0.000 title claims abstract description 202
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 239000011342 resin composition Substances 0.000 title description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 136
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 38
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 16
- 239000011164 primary particle Substances 0.000 claims abstract description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 8
- -1 silane compound Chemical class 0.000 claims description 135
- 239000003960 organic solvent Substances 0.000 claims description 117
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 66
- 229920005575 poly(amic acid) Polymers 0.000 claims description 52
- 239000002904 solvent Substances 0.000 claims description 52
- 239000000377 silicon dioxide Substances 0.000 claims description 45
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 33
- 229910000077 silane Inorganic materials 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 18
- 238000002296 dynamic light scattering Methods 0.000 claims description 18
- 238000009413 insulation Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229920001721 polyimide Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000004642 Polyimide Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 8
- 125000004423 acyloxy group Chemical group 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- 229910018540 Si C Inorganic materials 0.000 claims description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 239000002612 dispersion medium Substances 0.000 claims description 5
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004962 Polyamide-imide Substances 0.000 claims description 4
- 239000004697 Polyetherimide Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 229920003055 poly(ester-imide) Polymers 0.000 claims description 4
- 229920002312 polyamide-imide Polymers 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 150000004756 silanes Chemical class 0.000 claims description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 12
- 230000007062 hydrolysis Effects 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- 125000006033 1,1-dimethyl-2-propenyl group Chemical group 0.000 description 1
- 125000006034 1,2-dimethyl-1-propenyl group Chemical group 0.000 description 1
- 125000006035 1,2-dimethyl-2-propenyl group Chemical group 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- 125000006433 1-ethyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006438 1-i-propyl cyclopropyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006025 1-methyl-1-butenyl group Chemical group 0.000 description 1
- 125000006044 1-methyl-1-pentenyl group Chemical group 0.000 description 1
- 125000006019 1-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006028 1-methyl-2-butenyl group Chemical group 0.000 description 1
- 125000006048 1-methyl-2-pentenyl group Chemical group 0.000 description 1
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000006030 1-methyl-3-butenyl group Chemical group 0.000 description 1
- 125000006052 1-methyl-3-pentenyl group Chemical group 0.000 description 1
- 125000006055 1-methyl-4-pentenyl group Chemical group 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- 125000006439 1-n-propyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
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- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
Definitions
- the present invention relates to a silica sol and a resin composition containing a silicone compound, particularly an insulating resin composition.
- Insulating resin compositions containing silica particles and polyimide resin are used.
- a polyimide composition is prepared by mixing 1 to 70 parts by mass of alkoxysilane per 100 parts by mass of polyamic acid and water in an organic polar solvent, followed by dehydration and ring closure.
- a manufacturing method is disclosed (see Patent Document 1).
- a modified polyimide precursor solution in which all components are completely dissolved which is made by dissolving tetraalkoxysilane and pure water in a polyimide precursor solution, fine silica particles are generated in the polyimide resin.
- a finely dispersed silica polyimide enameled wire is disclosed.
- the present invention is aimed at improving the film-forming properties of an inorganic insulating film when producing a composition that is an insulating resin (hereinafter also referred to as a composition or an insulating resin composition) using a resin composition containing silica particles.
- the present invention aims to provide a silica particle-containing resin composition containing a silicone compound, and an insulating resin composition using the same. That is, the present invention is an organic solvent silica sol containing a silicone compound, and provides an insulating resin composition and an insulating coated conductive wire using the organic solvent silica sol.
- the formula (1) or formula (2) [In formula (1), R 1 , R 2 , R 3 , and R 4 each represent a methyl group or an ethyl group, and n1 represents a repeating unit.
- R 5 represents a methyl group or a phenyl group
- R 7 and R 8 each represent a methyl group or an ethyl group
- R 6 represents a methyl group, an ethyl group, or a formula (3):
- R 9 represents a methyl group or a phenyl group
- R 10 represents a methyl group, ethyl group, or a silicone compound
- R 11 represents a methyl group or an ethyl group
- n3 represents a repeating unit.
- * indicates a bonding site with an oxygen atom
- n2 indicates a repeating unit.
- the silicone compound-containing organic solvent silica sol according to the first aspect which contains a silicone compound represented by (representing a repeating unit);
- the silicone compound represented by R 10 in the above formula (3) is the formula (3-1), the formula (3-1) and the formula (3-2), or the formula (3-1) to the formula ( 3-3):
- R 31 represents a methyl group or a phenyl group
- R 32 represents a methyl group, ethyl group, or a group represented by formula (3-2)
- R 33 represents a methyl group or an ethyl group.
- R 34 represents a methyl group or a phenyl group
- R 35 represents a methyl group, an ethyl group, or a group represented by the formula (3-3)
- R 36 represents a methyl group.
- group or ethyl group in formula (3-3)
- R 37 represents a methyl group or phenyl group
- R 38 represents a methyl group or ethyl group
- R 39 represents a methyl group or ethyl group, n13
- the silicone compound-containing organic solvent silica sol according to the first aspect which contains the silicone compound shown in (n14 and n15 represent repeating units, * represents a bonding site with an oxygen atom).
- the silicone compound according to the first aspect or the second aspect wherein n1 of the silicone compound of formula (1) or (n11+n12) of the silicone compound of formula (4) has 4 to 15 repeating units.
- Containing organic solvent silica sol As a fifth aspect, the above repeating unit n2, (n2+n3), n13, n14 or n15 is represented by formula (2), or formula (3), formula (3-1), formula (3-2) and formula (3).
- the silicone compound-containing organic solvent according to the first or third aspect which is a repeating unit that meets the conditions of exhibiting a kinematic viscosity of 3 to 300 mm 2 /s at 25° C.
- silicone compound of formula (2) containing -3) silica sol As a sixth aspect, the silicone compound-containing organic solvent silica sol according to any one of the first to fifth aspects, wherein the content ratio of the silicone compound to SiO 2 in the organic solvent silica sol is 1 to 100% by mass. As a seventh aspect, the silicone compound-containing organic solvent according to any one of the first to fifth aspects, wherein the content ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol is 1 to 100% by mass.
- R 21 is an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, respectively.
- R22 each represents an alkoxy group, an acyloxy group, or a halogen group
- a represents an integer of 1 to 3
- R 23 and R 25 are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms, and are bonded to a silicon atom through a Si-C bond
- R 24 and R 26 each represent an alkoxy group, an acyloxy group, or a halogen group
- Y represents an alkylene group, an NH group, or an oxygen atom
- b is an integer from 1 to 3
- c is an integer of 0 or 1
- d is an integer of 1 to 3.
- the silicone compound-containing organic solvent silica sol according to any one of the first to seventh aspects which contains at least one silane compound selected from the group consisting of compounds represented by As a ninth aspect, the number of silicon atoms in the silane compounds of the above formulas (5) to (7) is coated on the surface of the silica particles from 0.3 atoms/nm 2 to 5.0 atoms/nm 2 .
- the silicone compound-containing organic solvent silica sol according to any one of the first to eighth aspects As a tenth aspect, the silicone compound-containing organic solvent silica sol according to any one of the first to ninth aspects, wherein the silicone compound or silane compound contains a covalent bond with a silica particle;
- the nitrogen-containing solvent is dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or N-ethylpyrrolidone
- the carbonyl group-containing oxygen-containing solvent is ⁇ -butyrolactone or cyclohexanone
- the sulfur-containing solvent is dimethyl
- the silicone compound-containing organic solvent silica sol according to any one of the first to twelfth aspects which is sulfoxide or dimethyl sulfone
- organic solvent silica sol As a fifteenth aspect, a composition comprising a silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer according to any one of the first to fourteenth aspects, As a 16th aspect, a composition that is an insulating resin containing a silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer according to any one of the 1st to 14th aspects; As a 17th aspect, in the 15th or 16th aspect, the amount of silica particles contained in the silicone compound-containing organic solvent silica sol is 0.01 to 1 part by mass with respect to 1 part by mass of the nitrogen-containing polymer.
- compositions described As an 18th aspect, the composition according to any one of the 15th to 17th aspects, wherein the nitrogen-containing polymer is polyimide, polyamide, polyamic acid, polyamideimide, polyetherimide, polyesterimide, or a mixture thereof.
- An insulating layer of 35 ⁇ m was formed, and a voltage (AC) of 3.0 kV (frequency 50 Hz) was applied between a disk electrode (25 mm in diameter) in close contact with the copper plate side and a spherical electrode (20 mm in diameter) in close contact with the insulating layer side.
- a composition having an insulation life of 85 minutes or more when measured at a temperature of 155°C As a 20th aspect, an insulated conductive wire in which the conductive wire is insulated and coated with the composition according to any one of the 15th to 19th aspects;
- step (A) preparing an alcohol solvent silica sol having 1 to 5 carbon atoms containing silica particles having an average primary particle diameter of 5 to 100 nm;
- step (B) A silane compound according to any one of formulas (5) to (7) is added to the silica sol obtained in step (A), and after the addition, at 20 to 100 ° C.
- the process of maintaining (C) step a step of replacing the alcohol solvent of the silica sol obtained in step (B) with a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent;
- the method for producing a silicone compound-containing organic solvent silica sol according to the first to fourteenth aspects includes a step (D) of adding a secondary or tertiary amine at a desired stage from the start of the step (B) to the end of the step (C).
- an alcohol solvent silica sol having 1 to 5 carbon atoms [organic solvent silica sol (i)] containing silica particles having an average primary particle diameter of 5 to 100 nm, and the above nitrogen-containing polymer [nitrogen-containing polymer (ii)] ] and the silicone compound [silicone compound (iii)] according to claim 1 or 2.
- step (E) is a step (E-1) of adding a silicone compound (iii) to the organic solvent silica sol (i) and further adding a nitrogen-containing polymer (ii); Step (E-2) of adding the nitrogen-containing polymer (ii) to the organic solvent silica sol (i) and further adding the silicone compound (iii), or adding the silicone compound (iii) to the nitrogen-containing polymer (ii),
- a method for producing a composition according to the 23rd aspect which is a step (E-3) of further adding an organic solvent silica sol (i)
- a method for producing the composition according to the twenty-fourth aspect including a step (F) of removing the organic solvent at a desired stage from the start of the (E) step to the end of the (E) step, and the twenty-sixth aspect.
- the present invention relates to an organic solvent silica sol containing a silicone compound, and an insulating resin composition and an insulated conductor using the same.
- insulating resin compositions that contain resins such as polyimide and polyamic acid and silica particles.
- the silica particles are added to the resin as an organic solvent silica sol, and after the organic solvent is removed, they are cured by heating or the like to form an insulating film in which the silica particles are dispersed in the resin.
- a silica insulating film is formed when the resin is eroded by the occurrence of electric discharge, and exhibits insulation properties.In the insulating film, the silica particles are close to each other, but since the silica particles exist alone, the silica Due to the deterioration of the film-forming properties of the insulating film, the gaps between the silica particles become paths for discharge phenomena, which may reach the surface of the base material and cause dielectric breakdown.
- the present invention uses an organic solvent silica sol containing a silicone oligomer to form an insulating resin composition and coats a base material to form an insulating film. It was found that the film-forming properties of the film were improved. Moreover, since silicone itself has high heat resistance and high insulation properties, it was found that the silica particles themselves and the gaps between the silica particles also have high insulation properties. In addition, in the present invention, the silica particles themselves are made hydrophobic by the silane compound, leading to improved dispersibility in organic solvents and improved compatibility with resins, so that they stably exist in the insulating resin composition, and can be applied to substrates. When this is done, film forming properties can be improved.
- the present invention is an organic solvent silica sol containing a silicone compound, which contains a silicone compound represented by formula (1) or formula (2) in an organic solvent silica sol containing silica particles having an average primary particle diameter of 5 to 100 nm.
- the above average primary particle diameter can be measured by the BET method (nitrogen gas adsorption method).
- R 1 , R 2 , R 3 and R 4 each represent a methyl group or an ethyl group, and n1 represents a repeating unit.
- R 1 , R 2 , R 3 and R 4 in formula (1) are all ethyl groups, it is called ethyl silicate.
- These silicates undergo hydrolysis and polycondensation with water in the presence of an acid or basic catalyst to form siloxane polymers, which function as a binder.
- silica particles act as a catalyst to cause hydrolysis and polycondensation of ethyl silicate, and can form graft bonds on the surface of the silica particles, coat the surfaces of the silica particles, or exist in the vicinity of the silica particles.
- R 1 , R 2 , R 3 , and R 4 each represent a methyl group or an ethyl group, and a mixture of methyl silicate oligomer and ethyl silicate oligomer can be used as formula (4).
- R 111 , R 112 , R 113 , and R 114 each represent an ethyl group
- R 115 , R 116 , R 117 , and R 118 each represent a methyl group
- n11 and n12 each represent a repeating group. Indicates the unit.
- silicone compound of formula (1) or formula (4) a silicone compound in which the repeating unit n1 or (n11+n12) is an integer of 5 to 10 can be used. These are oligomers, and the integer of 4 to 15 or 5 to 10 is the average value of the degree of polymerization of these silicone compounds, and can be used, for example, as an average pentamer or an average decamer.
- the viscosity of the silicone compound of formula (1) or formula (4), measured at 25° C., is, for example, in the range of 2 to 4 mPa ⁇ s for a pentameric compound and 13 to 24 mPa ⁇ s for a decameric compound. These are available as silicone compounds manufactured by Colcoat Co., Ltd.
- the silicone compound of formula (2) is a silicone compound obtained by hydrolysis and polycondensation of a silane compound having three hydrolyzable groups in one molecule.
- R 5 represents a methyl group or a phenyl group
- R 7 and R 8 each represent a methyl group or an ethyl group
- R 6 represents a methyl group, an ethyl group, or the formula (3).
- R 9 represents a methyl group or a phenyl group
- R 10 represents a methyl group, an ethyl group, or the formula (3-1)
- R 11 represents a methyl group or an ethyl group.
- R 6 is the formula (3) and R 10 is the formula (3-1)
- the side chain extends from the silicone main chain, and the side chain becomes the silicone main chain, and the side chain further extends from the main chain. It can have a multi-branched structure. For example, this corresponds to the case where R 32 in formula (3-1) is formula (3-2) and R 35 is formula (3-3).
- n2, (n2+n3), n13, n14 in the silicone compound of formula (2) or formula (3) containing formula (3-1), formula (3-2) and formula (3-3) or the integer of the repeating unit n15 is the above repeating unit in a range that exhibits a kinematic viscosity (25°C) of 3 to 300 mm 2 /s as a silicone compound of formula (2) or formula (2) containing formula (3) It can be expressed as an integer.
- These can be obtained by purchasing silicone compounds manufactured by Shin-Etsu Chemical Co., Ltd.
- the above-mentioned kinematic viscosity can be measured, for example, with a simple kinematic viscometer manufactured by STM Co., Ltd. under the trade name ASTM D7279.
- the silicone compounds of the above formulas (1), (2), and (4) can be used alone or in combination.
- the above-mentioned silicone compound can include at least a bond via a covalent bond with a silica particle.
- the ratio of the silicone compound to SiO 2 in the organic solvent silica sol can be in the range of 1 to 100% by mass, 1 to 70% by mass, 1 to 60% by mass, or 2 to 60% by mass.
- the ratio of the silicone compound to SiO 2 in the organic solvent silica sol containing the silicone compound is 1 to 100% by mass, 1 to 70% by mass, 1 to 60% by mass, 1 to 50% by mass, or 2 to 50% by mass. It can be contained within the range of.
- the silica particles can contain at least one silane compound selected from the group consisting of formulas (5) to (7).
- R 21 is an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group.
- R22 each represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 1 to 3;
- R 23 and R 25 are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms, and are bonded to a silicon atom through a Si-C bond.
- R 24 and R 26 each represent an alkoxy group, an acyloxy group, or a halogen group
- Y represents an alkylene group, an NH group, or an oxygen atom
- b is an integer from 1 to 3
- c is an integer of 0 or 1
- d is an integer of 1 to 3.
- the above alkyl group is an alkyl group having 1 to 18 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group.
- These include, but are not limited to:
- the alkylene group can be an alkylene group derived from the above-mentioned alkyl group.
- the above aryl group is an aryl group having 6 to 30 carbon atoms, and examples thereof include phenyl group, naphthyl group, anthracene group, and pyrene group.
- the alkenyl group is an alkenyl group having 2 to 10 carbon atoms, such as ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group.
- alkoxy group examples include alkoxy groups having 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t -butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2 -dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, etc., but are not limited to these.
- the above acyloxy group has 2 to 10 carbon atoms, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butyloxy group.
- halogen group examples include fluorine, chlorine, bromine, and iodine.
- organic group having an epoxy group examples include 2-(3,4-epoxycyclohexyl)ethyl group and 3-glycidoxypropyl group.
- the above (meth)acryloyl group represents both an acryloyl group and a methacryloyl group.
- the organic group having a (meth)acryloyl group include a 3-methacryloxypropyl group and a 3-acryloxypropyl group.
- An example of the organic group having a mercapto group is a 3-mercaptopropyl group.
- organic groups having an amino group include 2-aminoethyl group, 3-aminopropyl group, N-2-(aminoethyl)-3-aminopropyl group, and N-(1,3-dimethyl-butylidene)aminopropyl group.
- N-phenyl-3-aminopropyl group N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group, and the like.
- An example of the organic group having a ureido group is a 3-ureidopropyl group.
- An example of the organic group having a cyano group is a 3-cyanopropyl group.
- the above formulas (2) and (3) are preferably compounds that can form a trimethylsilyl group on the surface of the silica particles.
- R 12 is an alkoxy group, such as a methoxy group or an ethoxy group.
- silane compound a silane compound manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
- the reaction temperature can be from 20°C to the boiling point of the dispersion medium, for example from 20°C to 100°C.
- the reaction time can be about 0.1 to 6 hours.
- the number of silicon atoms in the silane compound is 0.3/nm 2 to 5.0/nm 2 or 0.6/nm 2 to 5.0 as the amount of coverage of the silica particle surface of the silane compound.
- the surface of the silica particles can be coated by containing a silane compound in the silica sol in a coating amount of 0.6/nm 2 or 0.6/nm 2 to 3.0/nm 2 .
- Water is required for hydrolysis of the above-mentioned silane compound, and if the sol is an aqueous solvent, such an aqueous solvent can be used. Water remaining in the solvent when the aqueous medium is replaced with an organic solvent such as methanol or ethanol can be used. For example, water present at 0.01 to 1% by weight can be used.
- hydrolysis can be carried out with or without a catalyst. When carrying out without a catalyst, the silica particle surface is present on the acidic side, and when using a catalyst, examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.
- Examples of the metal chelate compound as a hydrolysis catalyst include triethoxy mono(acetylacetonato) titanium and triethoxy mono(acetylacetonato) zirconium.
- Examples of organic acids as hydrolysis catalysts include acetic acid and oxalic acid.
- Examples of inorganic acids as hydrolysis catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
- Examples of organic bases used as hydrolysis catalysts include pyridine, pyrrole, piperazine, and quaternary ammonium salts.
- Examples of the inorganic base as a hydrolysis catalyst include ammonia, sodium hydroxide, and potassium hydroxide.
- the above-mentioned silane compound contains at least one bond via a covalent bond with the silica particle.
- the silica particles have aluminum atoms on the surface of the silica particles in an amount of 0.001 to 2.0 mass%/SiO 2 in terms of Al 2 O 3 , or 0.001 to 1.0 mass %/SiO 2 , or The silica particles can be bonded at a ratio of 0.001 to 0.5% by mass/SiO 2 or 0.001 to 0.3% by mass/SiO 2 .
- the amount of negative charge present on the silica particle surface increases, and is measured at, for example, 0.25 to 0.40 ⁇ eq/m 2 .
- a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent can be used as the organic solvent.
- nitrogen-containing solvents include dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, tetramethylurea, hexamethylphosphoric triamide, dimethylacrylamide, acryloylmorpholine, and hydroxyl.
- Ethylacrylamide isopropylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, dimethylaminopropylacrylamide methyl chloride quaternary salt, dimethylamino Examples include ethyl acrylate benzyl chloride quaternary salt.
- the nitrogen-containing solvent can be dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or N-ethylpyrrolidone.
- Examples of carbonyl group-containing oxygen-containing solvents include ketones and esters.
- the ketone is a linear or cyclic aliphatic ketone having 3 to 30 carbon atoms, such as methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and the like.
- Esters are linear or cyclic esters having 2 to 30 carbon atoms, such as ethyl acetate, n-butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, isopropyl acetate, ethyl lactate, lactic acid.
- Examples include butyl, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, phenyl acetate, phenyl lactate, phenyl propionate, and the like.
- the carbonyl group-containing oxygen-containing solvent is preferably ⁇ -butyrolactone or cyclohexanone.
- sulfur-containing solvents include dimethyl sulfoxide and dimethyl sulfone.
- amines can be added.
- examples of amines include secondary amines and tertiary amines having a total number of carbon atoms of 5 to 35.
- examples of the secondary amines include ethyl-n-propylamine, ethylisopropylamine, dipropylamine, diisopropylamine, ethylbutylamine, n-propylbutylamine, dibutylamine, ethylpentylamine, n-propylpentylamine, and isopropylpentylamine.
- tertiary amines include triethylamine, ethyldi-n-propylamine, diethyl-n-propylamine, tri-n-propylamine, triisopropylamine, ethyldibutylamine, diethylbutylamine, isopropyldibutylamine, diisopropylethylamine, diisopropyl
- examples include butylamine, tributylamine, ethyldipentylamine, diethylpentylamine, tripentylamine, methyldioctylamine, dimethyloctylamine, ethyldioctylamine, diethyloctylamine, trioctylamine,
- secondary amines and tertiary amines having an alkyl group having a total number of carbon atoms of 6 to 35 are preferred, such as diisopropylamine, tripentylamine, triisopropylamine, dimethyloctylamine, trioctylamine, etc. Can be mentioned. Furthermore, quaternary ammonium can be added.
- the quaternary ammonium hydroxide is preferably a tetraalkylammonium hydroxide having a total number of carbon atoms of 4 to 40.
- Examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-i-propylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, and the like.
- the present invention includes a composition containing the above-mentioned silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer.
- the above composition can be exemplified as an insulating composition.
- the nitrogen-containing polymer used in the present invention can be polyimide, polyamide, polyamic acid, polyamideimide, polyetherimide, polyesterimide, or a mixture thereof.
- Polyimide is a polymer obtained by imidizing aromatic diamine and aromatic tetracarboxylic dianhydride via polyamic acid.
- Polyamic acid can also be used as a polymer component of an insulating resin composition and converted into polyimide by heating during coating on a substrate.
- Polyamideimide, polyetherimide, and polyesterimide can be selected by selecting aromatic diamine and aromatic tetracarboxylic dianhydride.
- aromatic diamines that can be used as raw materials for the nitrogen-containing polymer include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, o-tolidine, o-dianidine, Examples include 1,5-diaminonaphthalene, 4,4'-diaminodiphenylsulfide, and 4,4'-diaminodiphenylsulfone.
- aromatic tetracarboxylic dianhydride used as a raw material for the nitrogen-containing polymer examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenone)propane dianhydride, bis (3,4-dicarboxyphenyl)ether dianhydride, ethylenetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, Examples include 4,4'-oxydiphthalic dianhydride.
- Preferred solvents in the reaction include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, tetramethylenesulfone, dimethylsulfone, pyridine, diethylene glycol dimethyl ether, and the like.
- the solvents can be used alone or in combination, or in combination with benzene, toluene, xylene, dioxane, butyrolactone, cyclohexane, and the like.
- Examples of dehydrating agents include aliphatic and aromatic carboxylic acid anhydrides such as acetic acid, propionic acid, isobutyric acid, benzoic acid, and propylbenzoic acid.
- Examples of imidization catalysts include tertiary amines such as pyridine, isoquinoline, 4-methylpyridine, and 3-methylpyridine.
- the organic solvent silica sol containing a silicone compound can have an average particle diameter of 5 to 100 nm as measured by dynamic light scattering (DLS). In the insulating resin composition, the amount of silica particles contained in the silicone compound-containing organic solvent silica sol can be 0.01 to 1 part by mass per 1 part by mass of the nitrogen-containing polymer.
- an insulated conductive wire is obtained in which a conductive wire is insulated and coated with the above-mentioned insulating resin composition.
- an insulating layer of the above insulating resin composition containing 7 to 30% by mass of silica was formed on a 0.5 mm thick copper plate to a thickness of 30 to 35 ⁇ m, and a disk electrode was placed in close contact with the copper plate. (diameter: 25 mm), insulation life is 85 minutes or more when measured under conditions of applied voltage (AC) of 3.0 kV, frequency of 50 Hz, and temperature of 155°C for a spherical electrode (diameter of 20 mm) that is in close contact with the insulating layer side.
- AC applied voltage
- the organic solvent silica sol of this case is manufactured by the following steps (A) to (C): (A) Step: preparing an alcohol solvent silica sol having 1 to 5 carbon atoms containing silica particles having an average primary particle diameter of 5 to 100 nm; (B) Step: A silane compound according to any one of formulas (5) to (7) is added to the silica sol obtained in step (A) at 20 to 100°C for 0.1 to 48 hours, or a step of carrying out a reaction for 0.1 to 6 hours; (C) Step: Production can include a step of replacing the silica sol obtained in Step (B) with a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent.
- step (A) examples include methanol, ethanol, n-propanol, i-propanol, n-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like.
- a step (D) of adding a secondary or tertiary amine can be added at any stage from the start of the step (B) to the end of the step (C).
- the insulating resin composition of the present invention comprises the alcohol solvent silica sol [organic solvent silica sol (i)], the nitrogen-containing polymer [nitrogen-containing polymer (ii)], and the above formula (1), formula (2), or It can be manufactured by including the step (E) of adding and mixing the silicone compound (iii) of formula (4).
- the order of addition of the organic solvent silica sol (i), the nitrogen-containing polymer (ii), and the silicone compound (iii) of the formula (1), formula (2), or formula (4) is at least three. Any order is possible as long as they are mixed.
- step (E) is a step (E-1) of adding a silicone compound (iii) to an organic solvent silica sol (i) and further adding a nitrogen-containing polymer (ii);
- the above-mentioned insulating resin composition can contain the organic solvent contained in the organic solvent silica sol, it is preferable to increase the solid content in the composition and improve the silica concentration in the coating film.
- E) It may include the step (F) of removing an organic solvent such as an alcohol, a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent at any stage from the start of the process to the end of the (E) process. preferable.
- the organic solvent silica sol (i) may or may not contain at least one silane compound selected from the group consisting of formulas (5) to (7), and may or may not contain at least one silane compound selected from the group consisting of formulas (5) to (7).
- Step 1 1000 g of water-dispersed silica sol (average primary particle size 12 nm, pH 2.5, silica concentration 20% by mass, Al2O3 concentration 0.42% by mass/ SiO2 , manufactured by Nissan Chemical Co., Ltd.) was placed in a stirrer, A glass reactor with an internal volume of 2 L equipped with a condenser, a thermometer, and two injection ports is charged, and while the sol in the reactor is kept boiling, methanol vapor generated in another boiler is poured into the reactor. Water was replaced by methanol while the liquid level was gradually raised by continuously blowing into the silica sol in the tank.
- DMAC dimethylacetamide
- DMAC-dispersed silica sol 1A (silica concentration 30.5% by mass, pH 4.6, viscosity (20°C) 5 mPa ⁇ s, water 0.1% by mass, methanol 0.1% by mass, dynamic light scattering particle size 18 nm) ) was obtained.
- step (c) of Reference Example 1 DMAC-dispersed silica sol 2A (silica concentration 30.5% by mass, pH 4.4, viscosity (20°C) 5 mPa ⁇ s, moisture 0.1% by mass, methanol 0.1% by mass, dynamic light scattering particle size 21nm)
- DMAC dimethylacetamide
- DMAC-dispersed silica sol 3A sica concentration 20.8% by mass, pH 4.0, viscosity (20°C) 2 mPa ⁇ s
- 0.2% by mass of water 0.4% by mass of methanol, and a dynamic light scattering particle size of 21 nm.
- Step (b) of Reference Example 1 and A methanol-dispersed silica sol (silica concentration: 30.5% by mass, pH: 4.2, moisture: 0.5% by mass, viscosity: 2 mPa ⁇ s) was obtained by replacing the solvent in a similar manner.
- 1,000 g of the above methanol sol was placed in a 2L eggplant flask, and DMAC (dimethylacetamide) was supplied while the solvent was evaporated off using a rotary evaporator at a reduced pressure of 450 to 110 Torr and a bath temperature of 85 to 125°C.
- DMAC-dispersed silica sol 4A (silica concentration 20.5% by mass, pH 4.9, viscosity (20°C) 3 mPa ⁇ s, water 0.2% by mass, methanol 0.6% by mass, dynamic light A particle size of 18 nm by scattering method was obtained.
- Example 1 To 100 g of DMAC-dispersed silica sol 1A obtained in Reference Example 1, ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name ethyl silicate 40, ethoxy group as the alkoxy group in general formula (1), average molecular weight 745) was added as a silicone compound component. , was a pentamer on average. Note that ethyl silicate 40 also includes SiO 2 ) 0.90 g was added. After shaking vigorously by hand about 10 times, the mixture was mixed for 1 hour at 23°C using a mix rotor (manufactured by As One Co., Ltd., trade name MR-5).
- a mix rotor manufactured by As One Co., Ltd., trade name MR-5
- a particle size of 22 nm and a SiO 2 concentration of 30.8% by mass were obtained.
- the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 2.8% by mass.
- the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 2.7% by mass.
- the above sol was added to the polyamic acid obtained in Reference Example 5 and mixed in a glass bottle so that the resin/SiO 2 ratio was 80/20, and the mixture was mixed with a vacuum defoaming machine (manufactured by EME, trade name: V-mini 300). By defoaming and stirring for 20 minutes, a silica-containing polyamic acid (insulating resin composition) was obtained.
- Example 2 The same procedure as in Example 1 was carried out except that the amount of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: ethyl silicate 40) was changed to 1.7 g. A particle size of 21 nm as determined by light scattering method and a SiO 2 concentration of 30.8% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 5.6% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 5.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
- ethyl silicate oligomer manufactured by Colcoat Co., Ltd., trade name: ethyl silicate 40
- Example 3 The same procedure as in Example 1 was carried out except that the amount of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethyl silicate 40) was changed to 4.3 g. A particle size of 25 nm as determined by light scattering method and a SiO 2 concentration of 30.4% by mass) was obtained.
- the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 14.0% by mass.
- the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 13.5% by mass.
- a silica-containing polyamic acid (insulating resin composition) was obtained.
- Example 4 The same procedure as in Example 1 was carried out except that the amount of ethylsilicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethylsilicate 40) was changed to 17.1 g. A particle size of 20 nm as determined by optical scattering method and a SiO 2 concentration of 31.4% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 56.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 46.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
- ethylsilicate oligomer manufactured by Colcoat Co., Ltd., trade name: Ethylsilicate 40
- Example 5 The silicone compound component of Example 1 was an ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name ethyl silicate 48, in the general formula (1), the alkoxy group was an ethoxy group, the average molecular weight was 1400, and the average was a decamer. ) Except that the amount was changed to 1.6 g, the same operation as in Example 1 was performed to obtain a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 20 nm, SiO 2 concentration: 30.3% by mass). Next, in the same manner as in Example 1, the mixture was mixed with polyamic acid to obtain a silica-containing polyamic acid. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 5.3% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 5.3% by mass.
- Example 6 The same procedure as in Example 1 was carried out except that the silicone compound component in Example 1 was changed to 3.3 g of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethyl Silicate 48), and a silicone compound-containing organic solvent silica sol ( A dynamic light scattering method particle size of 20 nm and SiO 2 concentration of 30.3% by mass) were obtained.
- the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 10.7% by mass.
- the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 10.4% by mass.
- a silica-containing polyamic acid insulating resin composition
- Example 7 The silicone compound component of Example 1 was converted into a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-213, having a methoxy group as an alkoxy group and a phenyl group and a methyl group as organic functional groups in the general formula (2), The operation was carried out in the same manner as in Example 1, except that the kinematic viscosity (25° C.) was changed to 16 mm 2 /s ) 17.2 g. .1% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 56.5% by mass.
- the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 48.8% by mass.
- a silica-containing polyamic acid (insulating resin composition) was obtained.
- Example 8 The silicone compound component of Example 1 was a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KC-89S, having a methoxy group as an alkoxy group and a methyl group as an organic functional group in the general formula (2), and having a kinematic viscosity ( 25°C) 5 mm 2 /s) 16.1 g, the same operation as in Example 1 was carried out, and a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 21 nm, SiO 2 concentration 33.0 mass) %) was obtained.
- the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 52.7% by mass.
- the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 42.0% by mass.
- a silica-containing polyamic acid (insulating resin composition) was obtained.
- Example 9 The silicone compound component of Example 1 was a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515, having a methoxy group as an alkoxy group and a methyl group as an organic functional group in the general formula (2), and having a kinematic viscosity ( 25° C.) 7 mm 2 /s) 2.1 g, the same operation was carried out as in Example 1, and a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 21 nm, SiO 2 concentration 30.1 mass) %) was obtained.
- the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 6.8% by mass.
- the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.7% by mass.
- a silica-containing polyamic acid (insulating resin composition) was obtained.
- Example 10 The same procedure as in Example 1 was carried out except that the silicone compound component in Example 1 was changed to 5.2 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515), and a silicone compound-containing organic solvent silica sol was prepared. (Dynamic light scattering particle size: 21 nm, SiO 2 concentration: 32.1% by mass). The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 17.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 15.3% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
- silicone oligomer manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515
- Example 11 By adding 2.1 g of silicone oligomer (trade name KR-515, manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 g of DMAC-dispersed silica sol 2A obtained in Reference Example 2, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 22 nm, SiO 2 concentration: 30.9% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 6.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.6% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
- silicone oligomer trade name KR-515, manufactured by Shin-Etsu Chemical Co., Ltd.
- Example 12 By adding 5.2 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515) to 100 g of DMAC-dispersed silica sol 2A obtained in Reference Example 2, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 21 nm, SiO 2 concentration: 32.3% by mass) was obtained. Next, in the same manner as in Example 1, the mixture was mixed with polyamic acid to obtain a silica-containing polyamic acid. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 17.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 15.2% by mass.
- silicone oligomer manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515
- Example 13 By adding 10.8 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KC-89S) to 100 g of DMAC-dispersed silica sol 3A obtained in Reference Example 3, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 20 nm, SiO 2 concentration 24.0% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 3A was 52.7% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 40.6% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
- silicone oligomer manufactured by Shin-Etsu Chemical Co., Ltd., trade name KC-89S
- Example 14 By adding 1.4 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515) to 100 g of DMAC-dispersed silica sol 4A obtained in Reference Example 4, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 21 nm, SiO 2 concentration: 21.1% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 4A was 6.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
- silicone oligomer manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515
- Example 1 A silica-containing polyamic acid was obtained by performing the same operation as in Example 1 without adding the silicone compound component to the DMAC-dispersed silica sol 2A obtained in Reference Example 2.
- the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 0% by mass.
- the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
- Example 2 A silica-blended polyamic acid (insulating resin composition) was obtained by performing the same operation as in Example 1 without adding a silicone compound component to DMAC-dispersed silica sol 3A obtained in Reference Example 3.
- the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 3A was 0% by mass.
- the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
- Example 3 A silica-blended polyamic acid (insulating resin composition) was obtained by performing the same operation as in Example 1 without adding the silicone compound component to DMAC-dispersed silica sol 4A obtained in Reference Example 4.
- the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 4A was 0% by mass.
- the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
- Example 4 Polyamic acid (insulating resin composition) was obtained without adding silica sol, silane compound, and silicone compound.
- (silicone) is the type of silicone compound used in the examples and corresponds to a silicone compound selected from formula (1), formula (2), and formula (3) shown in the general formula. It was something to do.
- (Silicone content A) indicates the content ratio of the silicone compound to SiO 2 in the organic solvent silica sol (before addition of the silicone compound of formula (1) or formula (2)), and the unit is mass %.
- (Silicone content B) indicates the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol (after addition of the silicone compound of formula (1) or formula (2)), and the unit is mass %.
- (Silane functional group) indicates the type of organic functional group of the silane compound selected from formulas (5) to (7) represented by the general formula to be coated on the silica particles. And (none) indicates the case where the above-mentioned silane compound was not added.
- (Resin content) indicates the ratio of silica particles contained in the organic solvent silica sol to 1 part by mass of the nitrogen-containing polymer (polyamic acid synthesized in Reference Example 5), and the unit is parts by mass. When it is zero, the case where no organic solvent silica sol is added is described.
- (insulation life) is determined by forming insulating layers made of the insulating resin compositions of Examples 1 to 14 and Comparative Examples 1 to 4 to a film thickness of 30 to 35 ⁇ m on a 0.5 mm thick copper plate.
- the insulation life was measured using a disk electrode (diameter 25 mm) closely attached to the copper plate side and a spherical electrode (diameter 20 mm diameter) closely attached to the insulating layer side at an applied voltage (AC) of 3.0 kV and a frequency of 50 Hz.
- the unit is the length (minutes) until dielectric breakdown occurs.
- the silica-containing polyamic acids (insulating resin compositions) obtained in Examples 1 to 14 improve the insulation life of cured films (insulating coatings) in which silica-containing polyimide is baked, compared to Comparative Examples 1 to 4. I was able to do that.
- Preparation and evaluation of enameled wire 13 kg of the polyamic acid obtained in Reference Example 5 was placed in a 20 L plastic container, and while stirring with a mechanical stirrer, the silicone obtained by the same method as the silicone compound-containing organic solvent silica sol described in Example 2.
- the above silica-containing polyamic acid was applied and baked onto a copper conductor (1.0 mm diameter), and an insulated wire having an insulating layer with a thickness of 34 ⁇ m was finally produced. Further, as Reference Example 6, the polyamic acid obtained in Reference Example 5 was coated and baked on a copper conductor (1.0 mm diameter) to produce an insulated wire having an insulating layer with a thickness of 36 ⁇ m.
- the flexibility and insulation life (Vt test) of the insulated wire obtained above were evaluated. The evaluation method and conditions are shown below.
- the flexibility test results show that the minimum winding diameter without cracking is the self-diameter (1d), the minimum winding diameter without cracking is twice the self-diameter (2d), and the minimum winding diameter without cracking is the self-diameter (2d). It is three times the diameter (3d), and it can be said that the smaller the minimum wrapping diameter d is, the better the flexibility is.
- Example 6 has a composition containing only a polyamic acid insulating resin varnish. The insulated wire obtained in Example 2 was able to significantly increase the insulation life while maintaining mechanical properties compared to the wire coated with silica-free polyamic acid.
- the present invention is an organic solvent silica sol containing a silicone compound, and provides an insulating resin composition and an insulated conductor using the same.
Abstract
[Problem] To provide: an organic solvent-dispersed silica sol which contains a silicone compound; a composition using the organic solvent-dispersed silica sol; and an insulated covered conductive wire. [Solution] A silicone compound-containing organic solvent-dispersed silica sol that is obtained by having an organic solvent-dispersed silica sol, which contains silica particles having an average primary particle diameter of 5 to 100 nm, to contain a silicone compound that is represented by formula (1) or formula (2).
(In formula (1), each of R1, R2, R3 and R4 represents a methyl group or an ethyl group; and n1 represents a repeating unit. In formula (2), R5 represents a methyl group or a phenyl group; each of R7 and R8 represents a methyl group or an ethyl group; R6 represents a methyl group, an ethyl group or formula (3) (wherein R9 represents a methyl group or a phenyl group; R10 represents a methyl group, an ethyl group or a silicone compound; R11 represents a methyl group or an ethyl group; n3 represents a repeating unit; and * represents a binding site for an oxygen atom); and n2 represents a repeating unit.)
Description
本発明はシリコーン化合物を含むシリカゾル及び樹脂組成物、特に絶縁性樹脂組成物に関する。
The present invention relates to a silica sol and a resin composition containing a silicone compound, particularly an insulating resin composition.
シリカ粒子とポリイミド樹脂を配合した絶縁性樹脂組成物が利用されている。
例えば、有機極性溶剤中でポリアミド酸とシリカ成分に換算してポリアミド酸１００質量部当たり１～７０質量部のアルコキシシランと水とを混合した後に脱水、閉環することを特徴とするポリイミド組成物の製造方法が開示されている（特許文献１参照）。
また、ポリイミド前駆体溶液にテトラアルコキシシラン、純水を溶解して成る全成分が完全に溶解した変性ポリイミド前駆体溶液を導体上に塗布、焼き付けすることにより、ポリイミド樹脂中にシリカ微粒子を生成させたことを特徴とするシリカ微分散ポリイミドエナメル線（特許文献２参照）が開示されている。
シリカ粒子含有樹脂組成物を用いて絶縁性樹脂組成物を作製する場合に、放電抑制はシリカ粒子に依存し絶縁性を高めるためにシリカ粒子の無機膜としての造膜性の向上が求められる。 Insulating resin compositions containing silica particles and polyimide resin are used.
For example, a polyimide composition is prepared by mixing 1 to 70 parts by mass of alkoxysilane per 100 parts by mass of polyamic acid and water in an organic polar solvent, followed by dehydration and ring closure. A manufacturing method is disclosed (see Patent Document 1).
In addition, by applying and baking a modified polyimide precursor solution in which all components are completely dissolved, which is made by dissolving tetraalkoxysilane and pure water in a polyimide precursor solution, fine silica particles are generated in the polyimide resin. A finely dispersed silica polyimide enameled wire (see Patent Document 2) is disclosed.
When producing an insulating resin composition using a silica particle-containing resin composition, discharge suppression depends on the silica particles, and in order to improve insulation, it is required to improve the film forming properties of the silica particles as an inorganic film.
例えば、有機極性溶剤中でポリアミド酸とシリカ成分に換算してポリアミド酸１００質量部当たり１～７０質量部のアルコキシシランと水とを混合した後に脱水、閉環することを特徴とするポリイミド組成物の製造方法が開示されている（特許文献１参照）。
また、ポリイミド前駆体溶液にテトラアルコキシシラン、純水を溶解して成る全成分が完全に溶解した変性ポリイミド前駆体溶液を導体上に塗布、焼き付けすることにより、ポリイミド樹脂中にシリカ微粒子を生成させたことを特徴とするシリカ微分散ポリイミドエナメル線（特許文献２参照）が開示されている。
シリカ粒子含有樹脂組成物を用いて絶縁性樹脂組成物を作製する場合に、放電抑制はシリカ粒子に依存し絶縁性を高めるためにシリカ粒子の無機膜としての造膜性の向上が求められる。 Insulating resin compositions containing silica particles and polyimide resin are used.
For example, a polyimide composition is prepared by mixing 1 to 70 parts by mass of alkoxysilane per 100 parts by mass of polyamic acid and water in an organic polar solvent, followed by dehydration and ring closure. A manufacturing method is disclosed (see Patent Document 1).
In addition, by applying and baking a modified polyimide precursor solution in which all components are completely dissolved, which is made by dissolving tetraalkoxysilane and pure water in a polyimide precursor solution, fine silica particles are generated in the polyimide resin. A finely dispersed silica polyimide enameled wire (see Patent Document 2) is disclosed.
When producing an insulating resin composition using a silica particle-containing resin composition, discharge suppression depends on the silica particles, and in order to improve insulation, it is required to improve the film forming properties of the silica particles as an inorganic film.
本発明はシリカ粒子含有樹脂組成物を用いて絶縁性樹脂である組成物（以下、組成物又は絶縁性樹脂組成物とも称す）を作製する場合に、無機絶縁膜の造膜性の向上のためにシリコーン化合物を含むシリカ粒子含有樹脂組成物と、それを用いた絶縁性樹脂組成物を提供しようとするものである。即ち、シリコーン化合物を含む有機溶媒シリカゾルであり、それらを用いた絶縁性樹脂組成物と絶縁被覆導線を提供するものである。
The present invention is aimed at improving the film-forming properties of an inorganic insulating film when producing a composition that is an insulating resin (hereinafter also referred to as a composition or an insulating resin composition) using a resin composition containing silica particles. The present invention aims to provide a silica particle-containing resin composition containing a silicone compound, and an insulating resin composition using the same. That is, the present invention is an organic solvent silica sol containing a silicone compound, and provides an insulating resin composition and an insulating coated conductive wire using the organic solvent silica sol.
本発明は第１観点として、５～１００ｎｍの平均一次粒子径を有するシリカ粒子を含む有機溶媒シリカゾルに、式（１）又は式（２）：
〔式（１）中、Ｒ１、Ｒ２、Ｒ３、及びＲ４はそれぞれメチル基、又はエチル基を示し、ｎ１は繰り返し単位を示す。
式（２）中、Ｒ５はメチル基又はフェニル基を示し、Ｒ７及びＲ８はそれぞれメチル基又はエチル基を示し、Ｒ６はメチル基、エチル基、又は式（３）：
（式（３）中、Ｒ９はメチル基又はフェニル基を示し、Ｒ１０はメチル基、エチル基、又はシリコーン化合物を示し、Ｒ１１はメチル基又はエチル基を示し、ｎ３は繰り返し単位を示し、※は酸素原子との結合部位を示す。）を示し、ｎ２は繰り返し単位を示す。〕で示されるシリコーン化合物を含むシリコーン化合物含有有機溶媒シリカゾル、
第２観点として、上記式（１）のシリコーン化合物が式（４）：
（式（４）中、Ｒ１１１、Ｒ１１２、Ｒ１１３、及びＲ１１４はそれぞれエチル基を示し、Ｒ１１５、Ｒ１１６、Ｒ１１７、及びＲ１１８はそれぞれメチル基を示し、ｎ１１及びｎ１２はそれぞれ繰り返し単位を示す。）で示されるシリコーン化合物を含む第１観点に記載のシリコーン化合物含有有機溶媒シリカゾル、
第３観点として、上記式（３）中のＲ１０が示すシリコーン化合物が、式（３－１）、式（３－１）及び式（３－２）又は式（３－１）乃至式（３－３）：
（式（３－１）中、Ｒ３１はメチル基又はフェニル基を示し、Ｒ３２はメチル基、エチル基、又は式（３－２）で示される基を示し、Ｒ３３はメチル基又はエチル基を示し、式（３－２）中、Ｒ３４はメチル基又はフェニル基を示し、Ｒ３５はメチル基、エチル基、又は式（３－３）で示される基を示し、Ｒ３６はメチル基又はエチル基を示し、式（３－３）中、Ｒ３７はメチル基又はフェニル基を示し、Ｒ３８はメチル基又はエチル基を示し、Ｒ３９はメチル基又はエチル基を示し、ｎ１３、ｎ１４及びｎ１５は繰り返し単位を示し、※は酸素原子との結合部位を示す。）に示されるシリコーン化合物を含む第１観点に記載のシリコーン化合物含有有機溶媒シリカゾル。
第４観点として、上記式（１）のシリコーン化合物のｎ１、又は式（４）のシリコーン化合物の（ｎ１１＋ｎ１２）の繰り返し単位が、４～１５である第１観点又は第２観点に記載のシリコーン化合物含有有機溶媒シリカゾル、
第５観点として、上記の繰り返し単位ｎ２、（ｎ２＋ｎ３）、ｎ１３、ｎ１４又はｎ１５は、式（２）、又は式（３）、式（３－１）、式（３－２）及び式（３－３）を含む式（２）のシリコーン化合物として２５℃で３～３００ｍｍ２／ｓの動粘度を示す条件に該当する繰り返し単位である第１観点又は第３観点に記載のシリコーン化合物含有有機溶媒シリカゾル、
第６観点として、上記有機溶媒シリカゾル中のＳｉＯ２に対するシリコーン化合物の含有割合が、１～１００質量％である第１観点乃至第５観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第７観点として、上記シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対するシリコーン化合物の含有割合が、１～１００質量％である第１観点乃至第５観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第８観点として、更に式（５）乃至式（７）：
（式（５）中、Ｒ２１はそれぞれアルキル基、ハロゲン化アルキル基、アルケニル基、アリール基、又はエポキシ基、（メタ）アクリロイル基、メルカプト基、アミノ基、ウレイド基もしくはシアノ基を有する有機基で且つＳｉ－Ｃ結合によりケイ素原子と結合しているものであり、Ｒ２２はそれぞれアルコキシ基、アシルオキシ基、又はハロゲン基を示し、ａは１～３の整数を示し、
式（６）及び式（７）中、Ｒ２３及びＲ２５はそれぞれ炭素原子数１～３のアルキル基、又は炭素原子数６～３０のアリール基で且つＳｉ－Ｃ結合によりケイ素原子と結合しているものであり、Ｒ２４及びＲ２６はそれぞれアルコキシ基、アシルオキシ基、又はハロゲン基を示し、Ｙはアルキレン基、ＮＨ基、又は酸素原子を示し、ｂは１～３の整数であり、ｃは０又は１の整数であり、ｄは１～３の整数である。）で示される化合物からなる群より選ばれる少なくとも１種のシラン化合物を含むものである第１観点乃至第７観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第９観点として、上記式（５）乃至式（７）のシラン化合物中のケイ素原子の個数が、シリカ粒子表面に０．３個／ｎｍ２～５．０個／ｎｍ２の被覆量である第１観点乃至第８観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第１０観点として、上記シリコーン化合物又はシラン化合物が、シリカ粒子との共有結合を含む第１観点乃至第９観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、 As a first aspect of the present invention, the formula (1) or formula (2):
[In formula (1), R 1 , R 2 , R 3 , and R 4 each represent a methyl group or an ethyl group, and n1 represents a repeating unit.
In formula (2), R 5 represents a methyl group or a phenyl group, R 7 and R 8 each represent a methyl group or an ethyl group, and R 6 represents a methyl group, an ethyl group, or a formula (3):
(In formula (3), R 9 represents a methyl group or a phenyl group, R 10 represents a methyl group, ethyl group, or a silicone compound, R 11 represents a methyl group or an ethyl group, and n3 represents a repeating unit. , * indicates a bonding site with an oxygen atom), and n2 indicates a repeating unit. ] A silicone compound-containing organic solvent silica sol containing a silicone compound represented by
As a second aspect, the silicone compound of the above formula (1) has the formula (4):
(In formula (4), R 111 , R 112 , R 113 , and R 114 each represent an ethyl group, R 115 , R 116 , R 117 , and R 118 each represent a methyl group, and n11 and n12 each represent a methyl group. The silicone compound-containing organic solvent silica sol according to the first aspect, which contains a silicone compound represented by (representing a repeating unit);
As a third aspect, the silicone compound represented by R 10 in the above formula (3) is the formula (3-1), the formula (3-1) and the formula (3-2), or the formula (3-1) to the formula ( 3-3):
(In formula (3-1), R 31 represents a methyl group or a phenyl group, R 32 represents a methyl group, ethyl group, or a group represented by formula (3-2), and R 33 represents a methyl group or an ethyl group. In the formula (3-2), R 34 represents a methyl group or a phenyl group, R 35 represents a methyl group, an ethyl group, or a group represented by the formula (3-3), and R 36 represents a methyl group. group or ethyl group, in formula (3-3), R 37 represents a methyl group or phenyl group, R 38 represents a methyl group or ethyl group, R 39 represents a methyl group or ethyl group, n13, The silicone compound-containing organic solvent silica sol according to the first aspect, which contains the silicone compound shown in (n14 and n15 represent repeating units, * represents a bonding site with an oxygen atom).
As a fourth aspect, the silicone compound according to the first aspect or the second aspect, wherein n1 of the silicone compound of formula (1) or (n11+n12) of the silicone compound of formula (4) has 4 to 15 repeating units. Containing organic solvent silica sol,
As a fifth aspect, the above repeating unit n2, (n2+n3), n13, n14 or n15 is represented by formula (2), or formula (3), formula (3-1), formula (3-2) and formula (3). The silicone compound-containing organic solvent according to the first or third aspect, which is a repeating unit that meets the conditions of exhibiting a kinematic viscosity of 3 to 300 mm 2 /s at 25° C. as a silicone compound of formula (2) containing -3) silica sol,
As a sixth aspect, the silicone compound-containing organic solvent silica sol according to any one of the first to fifth aspects, wherein the content ratio of the silicone compound to SiO 2 in the organic solvent silica sol is 1 to 100% by mass.
As a seventh aspect, the silicone compound-containing organic solvent according to any one of the first to fifth aspects, wherein the content ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol is 1 to 100% by mass. solvent silica sol,
As an eighth aspect, further, formulas (5) to (7):
(In formula (5), R 21 is an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, respectively. and is bonded to a silicon atom through a Si-C bond, R22 each represents an alkoxy group, an acyloxy group, or a halogen group, a represents an integer of 1 to 3,
In formula (6) and formula (7), R 23 and R 25 are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms, and are bonded to a silicon atom through a Si-C bond. R 24 and R 26 each represent an alkoxy group, an acyloxy group, or a halogen group, Y represents an alkylene group, an NH group, or an oxygen atom, b is an integer from 1 to 3, and c is an integer of 0 or 1, and d is an integer of 1 to 3. ) The silicone compound-containing organic solvent silica sol according to any one of the first to seventh aspects, which contains at least one silane compound selected from the group consisting of compounds represented by
As a ninth aspect, the number of silicon atoms in the silane compounds of the above formulas (5) to (7) is coated on the surface of the silica particles from 0.3 atoms/nm 2 to 5.0 atoms/nm 2 . The silicone compound-containing organic solvent silica sol according to any one of the first to eighth aspects,
As a tenth aspect, the silicone compound-containing organic solvent silica sol according to any one of the first to ninth aspects, wherein the silicone compound or silane compound contains a covalent bond with a silica particle;
式（２）中、Ｒ５はメチル基又はフェニル基を示し、Ｒ７及びＲ８はそれぞれメチル基又はエチル基を示し、Ｒ６はメチル基、エチル基、又は式（３）：
第２観点として、上記式（１）のシリコーン化合物が式（４）：
第３観点として、上記式（３）中のＲ１０が示すシリコーン化合物が、式（３－１）、式（３－１）及び式（３－２）又は式（３－１）乃至式（３－３）：
第４観点として、上記式（１）のシリコーン化合物のｎ１、又は式（４）のシリコーン化合物の（ｎ１１＋ｎ１２）の繰り返し単位が、４～１５である第１観点又は第２観点に記載のシリコーン化合物含有有機溶媒シリカゾル、
第５観点として、上記の繰り返し単位ｎ２、（ｎ２＋ｎ３）、ｎ１３、ｎ１４又はｎ１５は、式（２）、又は式（３）、式（３－１）、式（３－２）及び式（３－３）を含む式（２）のシリコーン化合物として２５℃で３～３００ｍｍ２／ｓの動粘度を示す条件に該当する繰り返し単位である第１観点又は第３観点に記載のシリコーン化合物含有有機溶媒シリカゾル、
第６観点として、上記有機溶媒シリカゾル中のＳｉＯ２に対するシリコーン化合物の含有割合が、１～１００質量％である第１観点乃至第５観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第７観点として、上記シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対するシリコーン化合物の含有割合が、１～１００質量％である第１観点乃至第５観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第８観点として、更に式（５）乃至式（７）：
式（６）及び式（７）中、Ｒ２３及びＲ２５はそれぞれ炭素原子数１～３のアルキル基、又は炭素原子数６～３０のアリール基で且つＳｉ－Ｃ結合によりケイ素原子と結合しているものであり、Ｒ２４及びＲ２６はそれぞれアルコキシ基、アシルオキシ基、又はハロゲン基を示し、Ｙはアルキレン基、ＮＨ基、又は酸素原子を示し、ｂは１～３の整数であり、ｃは０又は１の整数であり、ｄは１～３の整数である。）で示される化合物からなる群より選ばれる少なくとも１種のシラン化合物を含むものである第１観点乃至第７観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第９観点として、上記式（５）乃至式（７）のシラン化合物中のケイ素原子の個数が、シリカ粒子表面に０．３個／ｎｍ２～５．０個／ｎｍ２の被覆量である第１観点乃至第８観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第１０観点として、上記シリコーン化合物又はシラン化合物が、シリカ粒子との共有結合を含む第１観点乃至第９観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、 As a first aspect of the present invention, the formula (1) or formula (2):
In formula (2), R 5 represents a methyl group or a phenyl group, R 7 and R 8 each represent a methyl group or an ethyl group, and R 6 represents a methyl group, an ethyl group, or a formula (3):
As a second aspect, the silicone compound of the above formula (1) has the formula (4):
As a third aspect, the silicone compound represented by R 10 in the above formula (3) is the formula (3-1), the formula (3-1) and the formula (3-2), or the formula (3-1) to the formula ( 3-3):
As a fourth aspect, the silicone compound according to the first aspect or the second aspect, wherein n1 of the silicone compound of formula (1) or (n11+n12) of the silicone compound of formula (4) has 4 to 15 repeating units. Containing organic solvent silica sol,
As a fifth aspect, the above repeating unit n2, (n2+n3), n13, n14 or n15 is represented by formula (2), or formula (3), formula (3-1), formula (3-2) and formula (3). The silicone compound-containing organic solvent according to the first or third aspect, which is a repeating unit that meets the conditions of exhibiting a kinematic viscosity of 3 to 300 mm 2 /s at 25° C. as a silicone compound of formula (2) containing -3) silica sol,
As a sixth aspect, the silicone compound-containing organic solvent silica sol according to any one of the first to fifth aspects, wherein the content ratio of the silicone compound to SiO 2 in the organic solvent silica sol is 1 to 100% by mass.
As a seventh aspect, the silicone compound-containing organic solvent according to any one of the first to fifth aspects, wherein the content ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol is 1 to 100% by mass. solvent silica sol,
As an eighth aspect, further, formulas (5) to (7):
In formula (6) and formula (7), R 23 and R 25 are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms, and are bonded to a silicon atom through a Si-C bond. R 24 and R 26 each represent an alkoxy group, an acyloxy group, or a halogen group, Y represents an alkylene group, an NH group, or an oxygen atom, b is an integer from 1 to 3, and c is an integer of 0 or 1, and d is an integer of 1 to 3. ) The silicone compound-containing organic solvent silica sol according to any one of the first to seventh aspects, which contains at least one silane compound selected from the group consisting of compounds represented by
As a ninth aspect, the number of silicon atoms in the silane compounds of the above formulas (5) to (7) is coated on the surface of the silica particles from 0.3 atoms/nm 2 to 5.0 atoms/nm 2 . The silicone compound-containing organic solvent silica sol according to any one of the first to eighth aspects,
As a tenth aspect, the silicone compound-containing organic solvent silica sol according to any one of the first to ninth aspects, wherein the silicone compound or silane compound contains a covalent bond with a silica particle;
第１１観点として、上記シリカ粒子が、Ａｌ２Ｏ３に換算して０．００１～２．０質量％／ＳｉＯ２の割合でアルミニウム原子と結合した第１観点乃至第１０観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第１２観点として、上記シリコーン化合物含有有機溶媒シリカゾルの分散媒が、窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒である第１観点乃至第１１観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第１３観点として、上記窒素含有溶媒がジメチルアセトアミド、ジメチルホルムアミド、Ｎ－メチルピロリドン、又はＮ－エチルピロリドンであり、カルボニル基含有酸素含有溶媒がγ－ブチロラクトン、又はシクロヘキサノンであり、イオウ含有溶媒がジメチルスルホキシド、又はジメチルスルホンである第１観点乃至第１２観点のいずれか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第１４観点として、上記シリコーン化合物含有有機溶媒シリカゾル中のシリカ粒子の動的光散乱法による平均粒子径が５～１００ｎｍである第１観点乃至第１３観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第１５観点として、第１観点乃至第１４観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾルと窒素含有ポリマーとを含む組成物、
第１６観点として、第１観点乃至第１４観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾルと窒素含有ポリマーとを含む絶縁性樹脂である組成物、
第１７観点として、上記窒素含有ポリマーの１質量部に対し、上記シリコーン化合物含有有機溶媒シリカゾルに含まれるシリカ粒子の配合量が、０．０１～１質量部である第１５観点又は第１６観点に記載の組成物、
第１８観点として、上記窒素含有ポリマーが、ポリイミド、ポリアミド、ポリアミック酸、ポリアミドイミド、ポリエーテルイミド、ポリエステルイミド、又はこれらの混合物である第１５観点乃至第１７観点のいずれか一つに記載の組成物、
第１９観点として、シリカ配合量が７～３０質量％である第１５観点乃至第１８観点の何れか一つに記載の組成物を、０．５ｍｍ厚の銅板上に塗布して層厚３０～３５μｍの絶縁層を形成し、銅板側に密着した円盤電極（直径２５ｍｍ径）と絶縁層側に密着した球状電極（直径２０ｍｍ径）との間に電圧（交流）３．０ｋＶ（周波数５０Ｈｚ）を温度１５５℃とする条件で印加して測定したときの絶縁寿命が８５分以上である組成物、
第２０観点として、第１５観点乃至第１９観点の何れか一つに記載の組成物により導線を絶縁被覆した絶縁被覆導線、 As an eleventh aspect, any one of the first to tenth aspects, wherein the silica particles are bonded to aluminum atoms at a ratio of 0.001 to 2.0 mass%/SiO 2 in terms of Al 2 O 3 The silicone compound-containing organic solvent silica sol described in
As a twelfth aspect, the silicone according to any one of the first to eleventh aspects, wherein the dispersion medium of the silicone compound-containing organic solvent silica sol is a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent. compound-containing organic solvent silica sol,
As a thirteenth aspect, the nitrogen-containing solvent is dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or N-ethylpyrrolidone, the carbonyl group-containing oxygen-containing solvent is γ-butyrolactone or cyclohexanone, and the sulfur-containing solvent is dimethyl The silicone compound-containing organic solvent silica sol according to any one of the first to twelfth aspects, which is sulfoxide or dimethyl sulfone;
As a fourteenth aspect, the silicone compound-containing organic solvent silica sol according to any one of the first to thirteenth aspects, wherein the silica particles in the silicone compound-containing organic solvent silica sol have an average particle diameter of 5 to 100 nm as determined by a dynamic light scattering method. organic solvent silica sol,
As a fifteenth aspect, a composition comprising a silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer according to any one of the first to fourteenth aspects,
As a 16th aspect, a composition that is an insulating resin containing a silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer according to any one of the 1st to 14th aspects;
As a 17th aspect, in the 15th or 16th aspect, the amount of silica particles contained in the silicone compound-containing organic solvent silica sol is 0.01 to 1 part by mass with respect to 1 part by mass of the nitrogen-containing polymer. The composition described,
As an 18th aspect, the composition according to any one of the 15th to 17th aspects, wherein the nitrogen-containing polymer is polyimide, polyamide, polyamic acid, polyamideimide, polyetherimide, polyesterimide, or a mixture thereof. thing,
As a 19th aspect, the composition according to any one of the 15th to 18th aspects, in which the silica content is 7 to 30% by mass, is coated on a 0.5 mm thick copper plate to a layer thickness of 30 to 30% by mass. An insulating layer of 35 μm was formed, and a voltage (AC) of 3.0 kV (frequency 50 Hz) was applied between a disk electrode (25 mm in diameter) in close contact with the copper plate side and a spherical electrode (20 mm in diameter) in close contact with the insulating layer side. A composition having an insulation life of 85 minutes or more when measured at a temperature of 155°C,
As a 20th aspect, an insulated conductive wire in which the conductive wire is insulated and coated with the composition according to any one of the 15th to 19th aspects;
第１２観点として、上記シリコーン化合物含有有機溶媒シリカゾルの分散媒が、窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒である第１観点乃至第１１観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第１３観点として、上記窒素含有溶媒がジメチルアセトアミド、ジメチルホルムアミド、Ｎ－メチルピロリドン、又はＮ－エチルピロリドンであり、カルボニル基含有酸素含有溶媒がγ－ブチロラクトン、又はシクロヘキサノンであり、イオウ含有溶媒がジメチルスルホキシド、又はジメチルスルホンである第１観点乃至第１２観点のいずれか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第１４観点として、上記シリコーン化合物含有有機溶媒シリカゾル中のシリカ粒子の動的光散乱法による平均粒子径が５～１００ｎｍである第１観点乃至第１３観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾル、
第１５観点として、第１観点乃至第１４観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾルと窒素含有ポリマーとを含む組成物、
第１６観点として、第１観点乃至第１４観点の何れか一つに記載のシリコーン化合物含有有機溶媒シリカゾルと窒素含有ポリマーとを含む絶縁性樹脂である組成物、
第１７観点として、上記窒素含有ポリマーの１質量部に対し、上記シリコーン化合物含有有機溶媒シリカゾルに含まれるシリカ粒子の配合量が、０．０１～１質量部である第１５観点又は第１６観点に記載の組成物、
第１８観点として、上記窒素含有ポリマーが、ポリイミド、ポリアミド、ポリアミック酸、ポリアミドイミド、ポリエーテルイミド、ポリエステルイミド、又はこれらの混合物である第１５観点乃至第１７観点のいずれか一つに記載の組成物、
第１９観点として、シリカ配合量が７～３０質量％である第１５観点乃至第１８観点の何れか一つに記載の組成物を、０．５ｍｍ厚の銅板上に塗布して層厚３０～３５μｍの絶縁層を形成し、銅板側に密着した円盤電極（直径２５ｍｍ径）と絶縁層側に密着した球状電極（直径２０ｍｍ径）との間に電圧（交流）３．０ｋＶ（周波数５０Ｈｚ）を温度１５５℃とする条件で印加して測定したときの絶縁寿命が８５分以上である組成物、
第２０観点として、第１５観点乃至第１９観点の何れか一つに記載の組成物により導線を絶縁被覆した絶縁被覆導線、 As an eleventh aspect, any one of the first to tenth aspects, wherein the silica particles are bonded to aluminum atoms at a ratio of 0.001 to 2.0 mass%/SiO 2 in terms of Al 2 O 3 The silicone compound-containing organic solvent silica sol described in
As a twelfth aspect, the silicone according to any one of the first to eleventh aspects, wherein the dispersion medium of the silicone compound-containing organic solvent silica sol is a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent. compound-containing organic solvent silica sol,
As a thirteenth aspect, the nitrogen-containing solvent is dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or N-ethylpyrrolidone, the carbonyl group-containing oxygen-containing solvent is γ-butyrolactone or cyclohexanone, and the sulfur-containing solvent is dimethyl The silicone compound-containing organic solvent silica sol according to any one of the first to twelfth aspects, which is sulfoxide or dimethyl sulfone;
As a fourteenth aspect, the silicone compound-containing organic solvent silica sol according to any one of the first to thirteenth aspects, wherein the silica particles in the silicone compound-containing organic solvent silica sol have an average particle diameter of 5 to 100 nm as determined by a dynamic light scattering method. organic solvent silica sol,
As a fifteenth aspect, a composition comprising a silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer according to any one of the first to fourteenth aspects,
As a 16th aspect, a composition that is an insulating resin containing a silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer according to any one of the 1st to 14th aspects;
As a 17th aspect, in the 15th or 16th aspect, the amount of silica particles contained in the silicone compound-containing organic solvent silica sol is 0.01 to 1 part by mass with respect to 1 part by mass of the nitrogen-containing polymer. The composition described,
As an 18th aspect, the composition according to any one of the 15th to 17th aspects, wherein the nitrogen-containing polymer is polyimide, polyamide, polyamic acid, polyamideimide, polyetherimide, polyesterimide, or a mixture thereof. thing,
As a 19th aspect, the composition according to any one of the 15th to 18th aspects, in which the silica content is 7 to 30% by mass, is coated on a 0.5 mm thick copper plate to a layer thickness of 30 to 30% by mass. An insulating layer of 35 μm was formed, and a voltage (AC) of 3.0 kV (frequency 50 Hz) was applied between a disk electrode (25 mm in diameter) in close contact with the copper plate side and a spherical electrode (20 mm in diameter) in close contact with the insulating layer side. A composition having an insulation life of 85 minutes or more when measured at a temperature of 155°C,
As a 20th aspect, an insulated conductive wire in which the conductive wire is insulated and coated with the composition according to any one of the 15th to 19th aspects;
第２１観点として、下記（Ａ）～（Ｃ）工程：
（Ａ）工程：５～１００ｎｍの平均一次粒子径を有するシリカ粒子を含む炭素原子数１～５のアルコール溶媒シリカゾルを準備する工程、
（Ｂ）工程：（Ａ）工程で得られたシリカゾルに式（５）乃至式（７）の何れか１項に記載のシラン化合物を添加し、添加後２０～１００℃で０．１～４８時間、維持する工程、
（Ｃ）工程：（Ｂ）工程で得られたシリカゾルのアルコール溶媒を窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒に溶媒置換する工程、
を含む第１観点乃至第１４観点に記載のシリコーン化合物含有有機溶媒シリカゾルの製造方法、
第２２観点として、（Ｂ）工程開始～（Ｃ）工程終了後までの所望の段階において第２級又は第３級アミンを添加する工程（Ｄ）を含む第２１観点に記載のシリコーン化合物含有有機溶媒シリカゾルの製造方法、
第２３観点として、５～１００ｎｍの平均一次粒子径を有するシリカ粒子を含む炭素原子数１～５のアルコール溶媒シリカゾル〔有機溶媒シリカゾル（ｉ）〕と、上記窒素含有ポリマー〔窒素含有ポリマー（ｉｉ）〕と、請求項１又は請求項２に記載のシリコーン化合物〔シリコーン化合物（ｉｉｉ）〕とを混合する工程（Ｅ）を含む第１５観点乃至第１９観点の何れか一つに記載の組成物の製造方法、
第２４観点として、工程（Ｅ）の添加の順が、
上記有機溶媒シリカゾル（ｉ）にシリコーン化合物（ｉｉｉ）を添加し、更に窒素含有ポリマー（ｉｉ）を添加する工程（Ｅ－１）、
有機溶媒シリカゾル（ｉ）に窒素含有ポリマー（ｉｉ）を添加し、更にシリコーン化合物（ｉｉｉ）を添加する工程（Ｅ－２）、又は
窒素含有ポリマー（ｉｉ）にシリコーン化合物（ｉｉｉ）を添加し、更に有機溶媒シリカゾル（ｉ）を添加する工程（Ｅ－３）である第２３観点に記載の組成物の製造方法、
第２５観点として、（Ｅ）工程開始～（Ｅ）工程終了後までの所望の段階において有機溶媒を除去する（Ｆ）工程を含む第２４観点に記載の組成物の製造方法、及び
第２６観点として、上記有機溶媒シリカゾル（ｉ）が式（５）乃至式（７）からなる群より選ばれる少なくとも１種のシラン化合物を含むものである第２３観点乃至第２５観点の何れか一つに記載の組成物の製造方法である。 As the 21st aspect, the following steps (A) to (C):
(A) Step: preparing an alcohol solvent silica sol having 1 to 5 carbon atoms containing silica particles having an average primary particle diameter of 5 to 100 nm;
(B) Step: A silane compound according to any one of formulas (5) to (7) is added to the silica sol obtained in step (A), and after the addition, at 20 to 100 ° C. time, the process of maintaining
(C) step: a step of replacing the alcohol solvent of the silica sol obtained in step (B) with a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent;
The method for producing a silicone compound-containing organic solvent silica sol according to the first to fourteenth aspects,
As a twenty-second aspect, the silicone compound-containing organic compound according to the twenty-first aspect includes a step (D) of adding a secondary or tertiary amine at a desired stage from the start of the step (B) to the end of the step (C). Method for producing solvent silica sol,
As a 23rd aspect, an alcohol solvent silica sol having 1 to 5 carbon atoms [organic solvent silica sol (i)] containing silica particles having an average primary particle diameter of 5 to 100 nm, and the above nitrogen-containing polymer [nitrogen-containing polymer (ii)] ] and the silicone compound [silicone compound (iii)] according to claim 1 or 2. Production method,
As a twenty-fourth viewpoint, the order of addition in step (E) is
a step (E-1) of adding a silicone compound (iii) to the organic solvent silica sol (i) and further adding a nitrogen-containing polymer (ii);
Step (E-2) of adding the nitrogen-containing polymer (ii) to the organic solvent silica sol (i) and further adding the silicone compound (iii), or adding the silicone compound (iii) to the nitrogen-containing polymer (ii), A method for producing a composition according to the 23rd aspect, which is a step (E-3) of further adding an organic solvent silica sol (i),
As a twenty-fifth aspect, a method for producing the composition according to the twenty-fourth aspect, including a step (F) of removing the organic solvent at a desired stage from the start of the (E) step to the end of the (E) step, and the twenty-sixth aspect. The composition according to any one of the twenty-third to twenty-fifth aspects, wherein the organic solvent silica sol (i) contains at least one silane compound selected from the group consisting of formulas (5) to (7). It is a method of manufacturing things.
（Ａ）工程：５～１００ｎｍの平均一次粒子径を有するシリカ粒子を含む炭素原子数１～５のアルコール溶媒シリカゾルを準備する工程、
（Ｂ）工程：（Ａ）工程で得られたシリカゾルに式（５）乃至式（７）の何れか１項に記載のシラン化合物を添加し、添加後２０～１００℃で０．１～４８時間、維持する工程、
（Ｃ）工程：（Ｂ）工程で得られたシリカゾルのアルコール溶媒を窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒に溶媒置換する工程、
を含む第１観点乃至第１４観点に記載のシリコーン化合物含有有機溶媒シリカゾルの製造方法、
第２２観点として、（Ｂ）工程開始～（Ｃ）工程終了後までの所望の段階において第２級又は第３級アミンを添加する工程（Ｄ）を含む第２１観点に記載のシリコーン化合物含有有機溶媒シリカゾルの製造方法、
第２３観点として、５～１００ｎｍの平均一次粒子径を有するシリカ粒子を含む炭素原子数１～５のアルコール溶媒シリカゾル〔有機溶媒シリカゾル（ｉ）〕と、上記窒素含有ポリマー〔窒素含有ポリマー（ｉｉ）〕と、請求項１又は請求項２に記載のシリコーン化合物〔シリコーン化合物（ｉｉｉ）〕とを混合する工程（Ｅ）を含む第１５観点乃至第１９観点の何れか一つに記載の組成物の製造方法、
第２４観点として、工程（Ｅ）の添加の順が、
上記有機溶媒シリカゾル（ｉ）にシリコーン化合物（ｉｉｉ）を添加し、更に窒素含有ポリマー（ｉｉ）を添加する工程（Ｅ－１）、
有機溶媒シリカゾル（ｉ）に窒素含有ポリマー（ｉｉ）を添加し、更にシリコーン化合物（ｉｉｉ）を添加する工程（Ｅ－２）、又は
窒素含有ポリマー（ｉｉ）にシリコーン化合物（ｉｉｉ）を添加し、更に有機溶媒シリカゾル（ｉ）を添加する工程（Ｅ－３）である第２３観点に記載の組成物の製造方法、
第２５観点として、（Ｅ）工程開始～（Ｅ）工程終了後までの所望の段階において有機溶媒を除去する（Ｆ）工程を含む第２４観点に記載の組成物の製造方法、及び
第２６観点として、上記有機溶媒シリカゾル（ｉ）が式（５）乃至式（７）からなる群より選ばれる少なくとも１種のシラン化合物を含むものである第２３観点乃至第２５観点の何れか一つに記載の組成物の製造方法である。 As the 21st aspect, the following steps (A) to (C):
(A) Step: preparing an alcohol solvent silica sol having 1 to 5 carbon atoms containing silica particles having an average primary particle diameter of 5 to 100 nm;
(B) Step: A silane compound according to any one of formulas (5) to (7) is added to the silica sol obtained in step (A), and after the addition, at 20 to 100 ° C. time, the process of maintaining
(C) step: a step of replacing the alcohol solvent of the silica sol obtained in step (B) with a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent;
The method for producing a silicone compound-containing organic solvent silica sol according to the first to fourteenth aspects,
As a twenty-second aspect, the silicone compound-containing organic compound according to the twenty-first aspect includes a step (D) of adding a secondary or tertiary amine at a desired stage from the start of the step (B) to the end of the step (C). Method for producing solvent silica sol,
As a 23rd aspect, an alcohol solvent silica sol having 1 to 5 carbon atoms [organic solvent silica sol (i)] containing silica particles having an average primary particle diameter of 5 to 100 nm, and the above nitrogen-containing polymer [nitrogen-containing polymer (ii)] ] and the silicone compound [silicone compound (iii)] according to claim 1 or 2. Production method,
As a twenty-fourth viewpoint, the order of addition in step (E) is
a step (E-1) of adding a silicone compound (iii) to the organic solvent silica sol (i) and further adding a nitrogen-containing polymer (ii);
Step (E-2) of adding the nitrogen-containing polymer (ii) to the organic solvent silica sol (i) and further adding the silicone compound (iii), or adding the silicone compound (iii) to the nitrogen-containing polymer (ii), A method for producing a composition according to the 23rd aspect, which is a step (E-3) of further adding an organic solvent silica sol (i),
As a twenty-fifth aspect, a method for producing the composition according to the twenty-fourth aspect, including a step (F) of removing the organic solvent at a desired stage from the start of the (E) step to the end of the (E) step, and the twenty-sixth aspect. The composition according to any one of the twenty-third to twenty-fifth aspects, wherein the organic solvent silica sol (i) contains at least one silane compound selected from the group consisting of formulas (5) to (7). It is a method of manufacturing things.
本発明はシリコーン化合物を含む有機溶媒シリカゾルであり、それらを用いた絶縁性樹脂組成物と絶縁被覆導線に係る。ポリイミドやポリアミック酸等の樹脂と、シリカ粒子を配合する絶縁性樹脂組成物が存在する。金属等の導体を基材としてその上に絶縁性樹脂組成物を被覆して基材を絶縁膜で被覆した場合に、放電現象は絶縁膜で遮る事になるが、その要因はシリカ粒子の耐絶縁性に依存する事が大きい。
シリカ粒子は有機溶媒シリカゾルとして樹脂に添加され、有機溶媒を除去した後に加熱等によって硬化され、シリカ粒子が樹脂に分散した絶縁膜が形成される。放電の発生によって樹脂が侵食される際にシリカ絶縁膜が形成される事で絶縁性を発揮する絶縁膜中では、シリカ粒子間は近接しているがシリカ粒子が単独で存在するために、シリカ絶縁膜の造膜性悪化によりシリカ粒子間の間隙は放電現象の通り道となり、基材表面に到達し絶縁破壊を起こすことがある。
本発明はシリコーンオリゴマーを含む有機溶媒シリカゾルを用いて絶縁性樹脂組成物として、基材に被覆して絶縁膜とした時に、絶縁膜中のシリカ粒子表面にシリコーンオリゴマーがグラフト結合乃至付着によりシリカ絶縁膜の造膜性を向上させる事が分かった。しかも、シリコーン自体は耐熱性が高く絶縁性も高いために、シリカ粒子自体とシリカ粒子間の間隙においても、高い絶縁性を有する事が分かった。
また、本発明ではシリカ粒子自体がシラン化合物による疎水化によって有機溶媒への分散性向上や、樹脂への相溶性向上につながり、絶縁性樹脂組成物中で安定に存在し、基材への塗布した際により造膜性を向上させる事ができる。 The present invention relates to an organic solvent silica sol containing a silicone compound, and an insulating resin composition and an insulated conductor using the same. There are insulating resin compositions that contain resins such as polyimide and polyamic acid and silica particles. When a conductor such as a metal is used as a base material and the base material is covered with an insulating film by coating it with an insulating resin composition, the discharge phenomenon is blocked by the insulating film, but this is due to the resistance of the silica particles. A lot depends on insulation.
The silica particles are added to the resin as an organic solvent silica sol, and after the organic solvent is removed, they are cured by heating or the like to form an insulating film in which the silica particles are dispersed in the resin. A silica insulating film is formed when the resin is eroded by the occurrence of electric discharge, and exhibits insulation properties.In the insulating film, the silica particles are close to each other, but since the silica particles exist alone, the silica Due to the deterioration of the film-forming properties of the insulating film, the gaps between the silica particles become paths for discharge phenomena, which may reach the surface of the base material and cause dielectric breakdown.
The present invention uses an organic solvent silica sol containing a silicone oligomer to form an insulating resin composition and coats a base material to form an insulating film. It was found that the film-forming properties of the film were improved. Moreover, since silicone itself has high heat resistance and high insulation properties, it was found that the silica particles themselves and the gaps between the silica particles also have high insulation properties.
In addition, in the present invention, the silica particles themselves are made hydrophobic by the silane compound, leading to improved dispersibility in organic solvents and improved compatibility with resins, so that they stably exist in the insulating resin composition, and can be applied to substrates. When this is done, film forming properties can be improved.
シリカ粒子は有機溶媒シリカゾルとして樹脂に添加され、有機溶媒を除去した後に加熱等によって硬化され、シリカ粒子が樹脂に分散した絶縁膜が形成される。放電の発生によって樹脂が侵食される際にシリカ絶縁膜が形成される事で絶縁性を発揮する絶縁膜中では、シリカ粒子間は近接しているがシリカ粒子が単独で存在するために、シリカ絶縁膜の造膜性悪化によりシリカ粒子間の間隙は放電現象の通り道となり、基材表面に到達し絶縁破壊を起こすことがある。
本発明はシリコーンオリゴマーを含む有機溶媒シリカゾルを用いて絶縁性樹脂組成物として、基材に被覆して絶縁膜とした時に、絶縁膜中のシリカ粒子表面にシリコーンオリゴマーがグラフト結合乃至付着によりシリカ絶縁膜の造膜性を向上させる事が分かった。しかも、シリコーン自体は耐熱性が高く絶縁性も高いために、シリカ粒子自体とシリカ粒子間の間隙においても、高い絶縁性を有する事が分かった。
また、本発明ではシリカ粒子自体がシラン化合物による疎水化によって有機溶媒への分散性向上や、樹脂への相溶性向上につながり、絶縁性樹脂組成物中で安定に存在し、基材への塗布した際により造膜性を向上させる事ができる。 The present invention relates to an organic solvent silica sol containing a silicone compound, and an insulating resin composition and an insulated conductor using the same. There are insulating resin compositions that contain resins such as polyimide and polyamic acid and silica particles. When a conductor such as a metal is used as a base material and the base material is covered with an insulating film by coating it with an insulating resin composition, the discharge phenomenon is blocked by the insulating film, but this is due to the resistance of the silica particles. A lot depends on insulation.
The silica particles are added to the resin as an organic solvent silica sol, and after the organic solvent is removed, they are cured by heating or the like to form an insulating film in which the silica particles are dispersed in the resin. A silica insulating film is formed when the resin is eroded by the occurrence of electric discharge, and exhibits insulation properties.In the insulating film, the silica particles are close to each other, but since the silica particles exist alone, the silica Due to the deterioration of the film-forming properties of the insulating film, the gaps between the silica particles become paths for discharge phenomena, which may reach the surface of the base material and cause dielectric breakdown.
The present invention uses an organic solvent silica sol containing a silicone oligomer to form an insulating resin composition and coats a base material to form an insulating film. It was found that the film-forming properties of the film were improved. Moreover, since silicone itself has high heat resistance and high insulation properties, it was found that the silica particles themselves and the gaps between the silica particles also have high insulation properties.
In addition, in the present invention, the silica particles themselves are made hydrophobic by the silane compound, leading to improved dispersibility in organic solvents and improved compatibility with resins, so that they stably exist in the insulating resin composition, and can be applied to substrates. When this is done, film forming properties can be improved.
本発明は５～１００ｎｍの平均一次粒子径を有するシリカ粒子を含む有機溶媒シリカゾルに式（１）又は式（２）で示されるシリコーン化合物を含む上記シリコーン化合物含有有機溶媒シリカゾルである。上記平均一次粒子径はＢＥＴ法（窒素ガス吸着法）によって測定する事ができる。
式（１）中、Ｒ１、Ｒ２、Ｒ３、及びＲ４はそれぞれメチル基、又はエチル基を示し、ｎ１は繰り返し単位を示す。 The present invention is an organic solvent silica sol containing a silicone compound, which contains a silicone compound represented by formula (1) or formula (2) in an organic solvent silica sol containing silica particles having an average primary particle diameter of 5 to 100 nm. The above average primary particle diameter can be measured by the BET method (nitrogen gas adsorption method).
In formula (1), R 1 , R 2 , R 3 and R 4 each represent a methyl group or an ethyl group, and n1 represents a repeating unit.
式（１）中、Ｒ１、Ｒ２、Ｒ３、及びＲ４はそれぞれメチル基、又はエチル基を示し、ｎ１は繰り返し単位を示す。 The present invention is an organic solvent silica sol containing a silicone compound, which contains a silicone compound represented by formula (1) or formula (2) in an organic solvent silica sol containing silica particles having an average primary particle diameter of 5 to 100 nm. The above average primary particle diameter can be measured by the BET method (nitrogen gas adsorption method).
In formula (1), R 1 , R 2 , R 3 and R 4 each represent a methyl group or an ethyl group, and n1 represents a repeating unit.
式（１）においてＲ１、Ｒ２、Ｒ３、及びＲ４が全てエチル基である場合はエチルシリケートと呼ばれている。これらのシリケートは酸又は塩基性触媒の存在下で水により加水分解と重縮合を生じシロキサンポリマーを形成し、それらはバインダー機能を発揮する。本発明ではシリカ粒子が触媒となりエチルシリケートの加水分解と重縮合を生じ、シリカ粒子表面にグラフト結合を形成したり、シリカ粒子表面を被覆したり、近傍に存在する事ができる。式（１）中、Ｒ１、Ｒ２、Ｒ３、及びＲ４はそれぞれメチル基、又はエチル基を示し、式（４）としてメチルシリケートオリゴマーとエチルシリケートオリゴマーとの混合物を用いる事ができる。式（４）中、Ｒ１１１、Ｒ１１２、Ｒ１１３、及びＲ１１４はそれぞれエチル基を示し、Ｒ１１５、Ｒ１１６、Ｒ１１７、及びＲ１１８はそれぞれメチル基を示し、ｎ１１及びｎ１２はそれぞれ繰り返し単位を示す。
式（１）又は式（４）のシリコーン化合物はｎ１、又は（ｎ１１＋ｎ１２）の繰り返し単位が５～１０の整数であるシリコーン化合物を用いる事ができる。これらはオリゴマーであり、４～１５、又は５～１０の整数はそれらシリコーン化合物の重合度の平均値であり、例えば平均５量体、平均１０量体として用いることができる。
式（１）又は式（４）のシリコーン化合物の粘度は２５℃の測定で例えば５量体化合物で２～４ｍＰａ・ｓ、１０量体化合物で１３～２４ｍＰａ・ｓの範囲に存在する。これらはコルコート株式会社製のシリコーン化合物として入手する事が可能である。 When R 1 , R 2 , R 3 and R 4 in formula (1) are all ethyl groups, it is called ethyl silicate. These silicates undergo hydrolysis and polycondensation with water in the presence of an acid or basic catalyst to form siloxane polymers, which function as a binder. In the present invention, silica particles act as a catalyst to cause hydrolysis and polycondensation of ethyl silicate, and can form graft bonds on the surface of the silica particles, coat the surfaces of the silica particles, or exist in the vicinity of the silica particles. In formula (1), R 1 , R 2 , R 3 , and R 4 each represent a methyl group or an ethyl group, and a mixture of methyl silicate oligomer and ethyl silicate oligomer can be used as formula (4). In formula (4), R 111 , R 112 , R 113 , and R 114 each represent an ethyl group, R 115 , R 116 , R 117 , and R 118 each represent a methyl group, and n11 and n12 each represent a repeating group. Indicates the unit.
As the silicone compound of formula (1) or formula (4), a silicone compound in which the repeating unit n1 or (n11+n12) is an integer of 5 to 10 can be used. These are oligomers, and the integer of 4 to 15 or 5 to 10 is the average value of the degree of polymerization of these silicone compounds, and can be used, for example, as an average pentamer or an average decamer.
The viscosity of the silicone compound of formula (1) or formula (4), measured at 25° C., is, for example, in the range of 2 to 4 mPa·s for a pentameric compound and 13 to 24 mPa·s for a decameric compound. These are available as silicone compounds manufactured by Colcoat Co., Ltd.
式（１）又は式（４）のシリコーン化合物はｎ１、又は（ｎ１１＋ｎ１２）の繰り返し単位が５～１０の整数であるシリコーン化合物を用いる事ができる。これらはオリゴマーであり、４～１５、又は５～１０の整数はそれらシリコーン化合物の重合度の平均値であり、例えば平均５量体、平均１０量体として用いることができる。
式（１）又は式（４）のシリコーン化合物の粘度は２５℃の測定で例えば５量体化合物で２～４ｍＰａ・ｓ、１０量体化合物で１３～２４ｍＰａ・ｓの範囲に存在する。これらはコルコート株式会社製のシリコーン化合物として入手する事が可能である。 When R 1 , R 2 , R 3 and R 4 in formula (1) are all ethyl groups, it is called ethyl silicate. These silicates undergo hydrolysis and polycondensation with water in the presence of an acid or basic catalyst to form siloxane polymers, which function as a binder. In the present invention, silica particles act as a catalyst to cause hydrolysis and polycondensation of ethyl silicate, and can form graft bonds on the surface of the silica particles, coat the surfaces of the silica particles, or exist in the vicinity of the silica particles. In formula (1), R 1 , R 2 , R 3 , and R 4 each represent a methyl group or an ethyl group, and a mixture of methyl silicate oligomer and ethyl silicate oligomer can be used as formula (4). In formula (4), R 111 , R 112 , R 113 , and R 114 each represent an ethyl group, R 115 , R 116 , R 117 , and R 118 each represent a methyl group, and n11 and n12 each represent a repeating group. Indicates the unit.
As the silicone compound of formula (1) or formula (4), a silicone compound in which the repeating unit n1 or (n11+n12) is an integer of 5 to 10 can be used. These are oligomers, and the integer of 4 to 15 or 5 to 10 is the average value of the degree of polymerization of these silicone compounds, and can be used, for example, as an average pentamer or an average decamer.
The viscosity of the silicone compound of formula (1) or formula (4), measured at 25° C., is, for example, in the range of 2 to 4 mPa·s for a pentameric compound and 13 to 24 mPa·s for a decameric compound. These are available as silicone compounds manufactured by Colcoat Co., Ltd.
式（２）のシリコーン化合物は１分子中に３個の加水分解性基を有するシラン化合物の加水分解と重縮合によって得られるシリコーン化合物である。
式（２）中、Ｒ５はメチル基又はフェニル基を示し、Ｒ７及びＲ８はそれぞれメチル基又はエチル基を示し、Ｒ６はメチル基、エチル基、又は式（３）を示す。式（３）中、Ｒ９はメチル基又はフェニル基を示し、Ｒ１０はメチル基、エチル基、又は式（３－１）を示し、Ｒ１１はメチル基又はエチル基を示す。Ｒ６が式（３）であり、Ｒ１０が更に式（３－１）である場合はシリコーン主鎖から側鎖が伸び、更に側鎖がシリコーン主鎖となりその主鎖から更に側鎖が伸びる多分岐した枝分かれ構造を有することができる。例えば、式（３－１）のＲ３２が式（３－２）であり、Ｒ３５が式（３－３）の場合に相当する。 The silicone compound of formula (2) is a silicone compound obtained by hydrolysis and polycondensation of a silane compound having three hydrolyzable groups in one molecule.
In formula (2), R 5 represents a methyl group or a phenyl group, R 7 and R 8 each represent a methyl group or an ethyl group, and R 6 represents a methyl group, an ethyl group, or the formula (3). In formula (3), R 9 represents a methyl group or a phenyl group, R 10 represents a methyl group, an ethyl group, or the formula (3-1), and R 11 represents a methyl group or an ethyl group. When R 6 is the formula (3) and R 10 is the formula (3-1), the side chain extends from the silicone main chain, and the side chain becomes the silicone main chain, and the side chain further extends from the main chain. It can have a multi-branched structure. For example, this corresponds to the case where R 32 in formula (3-1) is formula (3-2) and R 35 is formula (3-3).
式（２）中、Ｒ５はメチル基又はフェニル基を示し、Ｒ７及びＲ８はそれぞれメチル基又はエチル基を示し、Ｒ６はメチル基、エチル基、又は式（３）を示す。式（３）中、Ｒ９はメチル基又はフェニル基を示し、Ｒ１０はメチル基、エチル基、又は式（３－１）を示し、Ｒ１１はメチル基又はエチル基を示す。Ｒ６が式（３）であり、Ｒ１０が更に式（３－１）である場合はシリコーン主鎖から側鎖が伸び、更に側鎖がシリコーン主鎖となりその主鎖から更に側鎖が伸びる多分岐した枝分かれ構造を有することができる。例えば、式（３－１）のＲ３２が式（３－２）であり、Ｒ３５が式（３－３）の場合に相当する。 The silicone compound of formula (2) is a silicone compound obtained by hydrolysis and polycondensation of a silane compound having three hydrolyzable groups in one molecule.
In formula (2), R 5 represents a methyl group or a phenyl group, R 7 and R 8 each represent a methyl group or an ethyl group, and R 6 represents a methyl group, an ethyl group, or the formula (3). In formula (3), R 9 represents a methyl group or a phenyl group, R 10 represents a methyl group, an ethyl group, or the formula (3-1), and R 11 represents a methyl group or an ethyl group. When R 6 is the formula (3) and R 10 is the formula (3-1), the side chain extends from the silicone main chain, and the side chain becomes the silicone main chain, and the side chain further extends from the main chain. It can have a multi-branched structure. For example, this corresponds to the case where R 32 in formula (3-1) is formula (3-2) and R 35 is formula (3-3).
式（２）、又は式（３）式（３－１）、式（３－２）及び式（３－３）を含む式（２）のシリコーン化合物における、ｎ２、（ｎ２＋ｎ３）、ｎ１３、ｎ１４又はｎ１５の繰り返し単位の整数は、式（２）、又は式（３）を含む式（２）のシリコーン化合物として３～３００ｍｍ２／ｓの動粘度（２５℃）を示す範囲にある上記繰り返し単位の整数で示す事ができる。これらは信越化学工業株式会社製のシリコーン化合物を購入することで入手する事ができる。上記動粘度は、例えば（株）エスティーエム社製、商品名ＡＳＴＭ Ｄ７２７９等の簡易動粘度計により測定する事ができる。
上記式（１）、式（２）、及び式（４）のシリコーン化合物は単独で、又は混合して用いる事ができる。上記シリコーン化合物が、少なくともシリカ粒子と共有結合を介した結合を含む事ができる。 n2, (n2+n3), n13, n14 in the silicone compound of formula (2) or formula (3) containing formula (3-1), formula (3-2) and formula (3-3) or the integer of the repeating unit n15 is the above repeating unit in a range that exhibits a kinematic viscosity (25°C) of 3 to 300 mm 2 /s as a silicone compound of formula (2) or formula (2) containing formula (3) It can be expressed as an integer. These can be obtained by purchasing silicone compounds manufactured by Shin-Etsu Chemical Co., Ltd. The above-mentioned kinematic viscosity can be measured, for example, with a simple kinematic viscometer manufactured by STM Co., Ltd. under the trade name ASTM D7279.
The silicone compounds of the above formulas (1), (2), and (4) can be used alone or in combination. The above-mentioned silicone compound can include at least a bond via a covalent bond with a silica particle.
上記式（１）、式（２）、及び式（４）のシリコーン化合物は単独で、又は混合して用いる事ができる。上記シリコーン化合物が、少なくともシリカ粒子と共有結合を介した結合を含む事ができる。 n2, (n2+n3), n13, n14 in the silicone compound of formula (2) or formula (3) containing formula (3-1), formula (3-2) and formula (3-3) or the integer of the repeating unit n15 is the above repeating unit in a range that exhibits a kinematic viscosity (25°C) of 3 to 300 mm 2 /s as a silicone compound of formula (2) or formula (2) containing formula (3) It can be expressed as an integer. These can be obtained by purchasing silicone compounds manufactured by Shin-Etsu Chemical Co., Ltd. The above-mentioned kinematic viscosity can be measured, for example, with a simple kinematic viscometer manufactured by STM Co., Ltd. under the trade name ASTM D7279.
The silicone compounds of the above formulas (1), (2), and (4) can be used alone or in combination. The above-mentioned silicone compound can include at least a bond via a covalent bond with a silica particle.
本発明では有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が１～１００質量％、１～７０質量％、１～６０質量％、又は２～６０質量％の範囲に含有する事ができる。
本発明ではシリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が１～１００質量％、１～７０質量％、１～６０質量％、１～５０質量％、又は２～５０質量％の範囲に含有する事ができる。
本発明ではシリカ粒子が式（５）乃至式（７）からなる群より選ばれる少なくとも１種のシラン化合物を含むことができる。 In the present invention, the ratio of the silicone compound to SiO 2 in the organic solvent silica sol can be in the range of 1 to 100% by mass, 1 to 70% by mass, 1 to 60% by mass, or 2 to 60% by mass.
In the present invention, the ratio of the silicone compound to SiO 2 in the organic solvent silica sol containing the silicone compound is 1 to 100% by mass, 1 to 70% by mass, 1 to 60% by mass, 1 to 50% by mass, or 2 to 50% by mass. It can be contained within the range of.
In the present invention, the silica particles can contain at least one silane compound selected from the group consisting of formulas (5) to (7).
本発明ではシリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が１～１００質量％、１～７０質量％、１～６０質量％、１～５０質量％、又は２～５０質量％の範囲に含有する事ができる。
本発明ではシリカ粒子が式（５）乃至式（７）からなる群より選ばれる少なくとも１種のシラン化合物を含むことができる。 In the present invention, the ratio of the silicone compound to SiO 2 in the organic solvent silica sol can be in the range of 1 to 100% by mass, 1 to 70% by mass, 1 to 60% by mass, or 2 to 60% by mass.
In the present invention, the ratio of the silicone compound to SiO 2 in the organic solvent silica sol containing the silicone compound is 1 to 100% by mass, 1 to 70% by mass, 1 to 60% by mass, 1 to 50% by mass, or 2 to 50% by mass. It can be contained within the range of.
In the present invention, the silica particles can contain at least one silane compound selected from the group consisting of formulas (5) to (7).
式（５）中、Ｒ２１はそれぞれアルキル基、ハロゲン化アルキル基、アルケニル基、アリール基、又はエポキシ基、（メタ）アクリロイル基、メルカプト基、アミノ基、ウレイド基、もしくはシアノ基を有する有機基で且つＳｉ－Ｃ結合によりケイ素原子と結合しているものであって、Ｒ２２はそれぞれアルコキシ基、アシルオキシ基、又はハロゲン基を示し、ａは１～３の整数を示し、
式（６）及び式（７）中、Ｒ２３及びＲ２５はそれぞれ炭素原子数１～３のアルキル基、又は炭素原子数６～３０のアリール基で且つＳｉ－Ｃ結合によりケイ素原子と結合しているものであり、Ｒ２４及びＲ２６はそれぞれアルコキシ基、アシルオキシ基、又はハロゲン基を示し、Ｙはアルキレン基、ＮＨ基、又は酸素原子を示し、ｂは１～３の整数であり、ｃは０又は１の整数であり、ｄは１～３の整数である。上記アルキル基は炭素原子数１～１８のアルキル基であり、例えばメチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、シクロプロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、シクロブチル基、１－メチル－シクロプロピル基、２－メチル－シクロプロピル基、ｎ－ペンチル基、１－メチル－ｎ－ブチル基、２－メチル－ｎ－ブチル基、３－メチル－ｎ－ブチル基、１，１－ジメチル－ｎ－プロピル基、１，２－ジメチル－ｎ－プロピル基、２，２－ジメチル－ｎ－プロピル基、１－エチル－ｎ－プロピル基、シクロペンチル基、１－メチル－シクロブチル基、２－メチル－シクロブチル基、３－メチル－シクロブチル基、１，２－ジメチル－シクロプロピル基、２，３－ジメチル－シクロプロピル基、１－エチル－シクロプロピル基、２－エチル－シクロプロピル基、ｎ－ヘキシル基、１－メチル－ｎ－ペンチル基、２－メチル－ｎ－ペンチル基、３－メチル－ｎ－ペンチル基、４－メチル－ｎ－ペンチル基、１，１－ジメチル－ｎ－ブチル基、１，２－ジメチル－ｎ－ブチル基、１，３－ジメチル－ｎ－ブチル基、２，２－ジメチル－ｎ－ブチル基、２，３－ジメチル－ｎ－ブチル基、３，３－ジメチル－ｎ－ブチル基、１－エチル－ｎ－ブチル基、２－エチル－ｎ－ブチル基、１，１，２－トリメチル－ｎ－プロピル基、１，２，２－トリメチル－ｎ－プロピル基、１－エチル－１－メチル－ｎ－プロピル基、１－エチル－２－メチル－ｎ－プロピル基、シクロヘキシル基、１－メチル－シクロペンチル基、２－メチル－シクロペンチル基、３－メチル－シクロペンチル基、１－エチル－シクロブチル基、２－エチル－シクロブチル基、３－エチル－シクロブチル基、１，２－ジメチル－シクロブチル基、１，３－ジメチル－シクロブチル基、２，２－ジメチル－シクロブチル基、２，３－ジメチル－シクロブチル基、２，４－ジメチル－シクロブチル基、３，３－ジメチル－シクロブチル基、１－ｎ－プロピル－シクロプロピル基、２－ｎ－プロピル－シクロプロピル基、１－ｉ－プロピル－シクロプロピル基、２－ｉ－プロピル－シクロプロピル基、１，２，２－トリメチル－シクロプロピル基、１，２，３－トリメチル－シクロプロピル基、２，２，３－トリメチル－シクロプロピル基、１－エチル－２－メチル－シクロプロピル基、２－エチル－１－メチル－シクロプロピル基、２－エチル－２－メチル－シクロプロピル基及び２－エチル－３－メチル－シクロプロピル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等があげられるが、これらに限定されない。 In formula (5), R 21 is an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group. and is bonded to a silicon atom through a Si-C bond, R22 each represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 1 to 3;
In formula (6) and formula (7), R 23 and R 25 are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms, and are bonded to a silicon atom through a Si-C bond. R 24 and R 26 each represent an alkoxy group, an acyloxy group, or a halogen group, Y represents an alkylene group, an NH group, or an oxygen atom, b is an integer from 1 to 3, and c is an integer of 0 or 1, and d is an integer of 1 to 3. The above alkyl group is an alkyl group having 1 to 18 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group. group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3 -Methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, Cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group , 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl -n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1, 2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl -cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n- Propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-2-methyl-cyclopropyl group. Ethyl-3-methyl-cyclopropyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. These include, but are not limited to:
式（６）及び式（７）中、Ｒ２３及びＲ２５はそれぞれ炭素原子数１～３のアルキル基、又は炭素原子数６～３０のアリール基で且つＳｉ－Ｃ結合によりケイ素原子と結合しているものであり、Ｒ２４及びＲ２６はそれぞれアルコキシ基、アシルオキシ基、又はハロゲン基を示し、Ｙはアルキレン基、ＮＨ基、又は酸素原子を示し、ｂは１～３の整数であり、ｃは０又は１の整数であり、ｄは１～３の整数である。上記アルキル基は炭素原子数１～１８のアルキル基であり、例えばメチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、シクロプロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、シクロブチル基、１－メチル－シクロプロピル基、２－メチル－シクロプロピル基、ｎ－ペンチル基、１－メチル－ｎ－ブチル基、２－メチル－ｎ－ブチル基、３－メチル－ｎ－ブチル基、１，１－ジメチル－ｎ－プロピル基、１，２－ジメチル－ｎ－プロピル基、２，２－ジメチル－ｎ－プロピル基、１－エチル－ｎ－プロピル基、シクロペンチル基、１－メチル－シクロブチル基、２－メチル－シクロブチル基、３－メチル－シクロブチル基、１，２－ジメチル－シクロプロピル基、２，３－ジメチル－シクロプロピル基、１－エチル－シクロプロピル基、２－エチル－シクロプロピル基、ｎ－ヘキシル基、１－メチル－ｎ－ペンチル基、２－メチル－ｎ－ペンチル基、３－メチル－ｎ－ペンチル基、４－メチル－ｎ－ペンチル基、１，１－ジメチル－ｎ－ブチル基、１，２－ジメチル－ｎ－ブチル基、１，３－ジメチル－ｎ－ブチル基、２，２－ジメチル－ｎ－ブチル基、２，３－ジメチル－ｎ－ブチル基、３，３－ジメチル－ｎ－ブチル基、１－エチル－ｎ－ブチル基、２－エチル－ｎ－ブチル基、１，１，２－トリメチル－ｎ－プロピル基、１，２，２－トリメチル－ｎ－プロピル基、１－エチル－１－メチル－ｎ－プロピル基、１－エチル－２－メチル－ｎ－プロピル基、シクロヘキシル基、１－メチル－シクロペンチル基、２－メチル－シクロペンチル基、３－メチル－シクロペンチル基、１－エチル－シクロブチル基、２－エチル－シクロブチル基、３－エチル－シクロブチル基、１，２－ジメチル－シクロブチル基、１，３－ジメチル－シクロブチル基、２，２－ジメチル－シクロブチル基、２，３－ジメチル－シクロブチル基、２，４－ジメチル－シクロブチル基、３，３－ジメチル－シクロブチル基、１－ｎ－プロピル－シクロプロピル基、２－ｎ－プロピル－シクロプロピル基、１－ｉ－プロピル－シクロプロピル基、２－ｉ－プロピル－シクロプロピル基、１，２，２－トリメチル－シクロプロピル基、１，２，３－トリメチル－シクロプロピル基、２，２，３－トリメチル－シクロプロピル基、１－エチル－２－メチル－シクロプロピル基、２－エチル－１－メチル－シクロプロピル基、２－エチル－２－メチル－シクロプロピル基及び２－エチル－３－メチル－シクロプロピル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等があげられるが、これらに限定されない。 In formula (5), R 21 is an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group. and is bonded to a silicon atom through a Si-C bond, R22 each represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 1 to 3;
In formula (6) and formula (7), R 23 and R 25 are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms, and are bonded to a silicon atom through a Si-C bond. R 24 and R 26 each represent an alkoxy group, an acyloxy group, or a halogen group, Y represents an alkylene group, an NH group, or an oxygen atom, b is an integer from 1 to 3, and c is an integer of 0 or 1, and d is an integer of 1 to 3. The above alkyl group is an alkyl group having 1 to 18 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group. group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3 -Methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, Cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group , 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl -n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1, 2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl -cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n- Propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-2-methyl-cyclopropyl group. Ethyl-3-methyl-cyclopropyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. These include, but are not limited to:
また、アルキレン基は上述のアルキル基から誘導されるアルキレン基を上げる事ができる。
上記アリール基は炭素原子数６～３０のアリール基であり例えば、フェニル基、ナフチル基、アントラセン基、ピレン基等が挙げられる。
アルケニル基としては炭素数２～１０のアルケニル基であり、エテニル基、１－プロペニル基、２－プロペニル基、１－メチル－１－エテニル基、１－ブテニル基、２－ブテニル基、３－ブテニル基、２－メチル－１－プロペニル基、２－メチル－２－プロペニル基、１－エチルエテニル基、１－メチル－１－プロペニル基、１－メチル－２－プロペニル基、１－ペンテニル基、２－ペンテニル基、３－ペンテニル基、４－ペンテニル基、１－ｎ－プロピルエテニル基、１－メチル－１－ブテニル基、１－メチル－２－ブテニル基、１－メチル－３－ブテニル基、２－エチル－２－プロペニル基、２－メチル－１－ブテニル基、２－メチル－２－ブテニル基、２－メチル－３－ブテニル基、３－メチル－１－ブテニル基、３－メチル－２－ブテニル基、３－メチル－３－ブテニル基、１，１－ジメチル－２－プロペニル基、１－ｉ－プロピルエテニル基、１，２－ジメチル－１－プロペニル基、１，２－ジメチル－２－プロペニル基、１－シクロペンテニル基、２－シクロペンテニル基、３－シクロペンテニル基、１－ヘキセニル基、２－ヘキセニル基、３－ヘキセニル基、４－ヘキセニル基、５－ヘキセニル基、１－メチル－１－ペンテニル基、１－メチル－２－ペンテニル基、１－メチル－３－ペンテニル基、１－メチル－４－ペンテニル基、１－ｎ－ブチルエテニル基、２－メチル－１－ペンテニル基、２－メチル－２－ペンテニル基等が挙げられるが、これらに限定されない。 Further, the alkylene group can be an alkylene group derived from the above-mentioned alkyl group.
The above aryl group is an aryl group having 6 to 30 carbon atoms, and examples thereof include phenyl group, naphthyl group, anthracene group, and pyrene group.
The alkenyl group is an alkenyl group having 2 to 10 carbon atoms, such as ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group. group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2- Pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2 -Ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2- Butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2 -Propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl -1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2 Examples include, but are not limited to, -methyl-2-pentenyl group.
上記アリール基は炭素原子数６～３０のアリール基であり例えば、フェニル基、ナフチル基、アントラセン基、ピレン基等が挙げられる。
アルケニル基としては炭素数２～１０のアルケニル基であり、エテニル基、１－プロペニル基、２－プロペニル基、１－メチル－１－エテニル基、１－ブテニル基、２－ブテニル基、３－ブテニル基、２－メチル－１－プロペニル基、２－メチル－２－プロペニル基、１－エチルエテニル基、１－メチル－１－プロペニル基、１－メチル－２－プロペニル基、１－ペンテニル基、２－ペンテニル基、３－ペンテニル基、４－ペンテニル基、１－ｎ－プロピルエテニル基、１－メチル－１－ブテニル基、１－メチル－２－ブテニル基、１－メチル－３－ブテニル基、２－エチル－２－プロペニル基、２－メチル－１－ブテニル基、２－メチル－２－ブテニル基、２－メチル－３－ブテニル基、３－メチル－１－ブテニル基、３－メチル－２－ブテニル基、３－メチル－３－ブテニル基、１，１－ジメチル－２－プロペニル基、１－ｉ－プロピルエテニル基、１，２－ジメチル－１－プロペニル基、１，２－ジメチル－２－プロペニル基、１－シクロペンテニル基、２－シクロペンテニル基、３－シクロペンテニル基、１－ヘキセニル基、２－ヘキセニル基、３－ヘキセニル基、４－ヘキセニル基、５－ヘキセニル基、１－メチル－１－ペンテニル基、１－メチル－２－ペンテニル基、１－メチル－３－ペンテニル基、１－メチル－４－ペンテニル基、１－ｎ－ブチルエテニル基、２－メチル－１－ペンテニル基、２－メチル－２－ペンテニル基等が挙げられるが、これらに限定されない。 Further, the alkylene group can be an alkylene group derived from the above-mentioned alkyl group.
The above aryl group is an aryl group having 6 to 30 carbon atoms, and examples thereof include phenyl group, naphthyl group, anthracene group, and pyrene group.
The alkenyl group is an alkenyl group having 2 to 10 carbon atoms, such as ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group. group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2- Pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2 -Ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2- Butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2 -Propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl -1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2 Examples include, but are not limited to, -methyl-2-pentenyl group.
上記アルコキシ基は炭素原子数１～１０のアルコキシ基が挙げられ、例えばメトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｉ－ブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基、ｎ－ペンチロキシ基、１－メチル－ｎ－ブトキシ基、２－メチル－ｎ－ブトキシ基、３－メチル－ｎ－ブトキシ基、１，１－ジメチル－ｎ－プロポキシ基、１，２－ジメチル－ｎ－プロポキシ基、２，２－ジメチル－ｎ－プロポキシ基、１－エチル－ｎ－プロポキシ基、ｎ－ヘキシロキシ基等が挙げられるが、これらに限定されない。
上記アシルオキシ基は炭素原子数２～１０のアシルオキシ基は、例えばメチルカルボニルオキシ基、エチルカルボニルオキシ基、ｎ－プロピルカルボニルオキシ基、ｉ－プロピルカルボニルオキシ基、ｎ－ブチルカルボニルオキシ基、ｉ－ブチルカルボニルオキシ基、ｓ－ブチルカルボニルオキシ基、ｔ－ブチルカルボニルオキシ基、ｎ－ペンチルカルボニルオキシ基、１－メチル－ｎ－ブチルカルボニルオキシ基、２－メチル－ｎ－ブチルカルボニルオキシ基、３－メチル－ｎ－ブチルカルボニルオキシ基、１，１－ジメチル－ｎ－プロピルカルボニルオキシ基、１，２－ジメチル－ｎ－プロピルカルボニルオキシ基、２，２－ジメチル－ｎ－プロピルカルボニルオキシ基、１－エチル－ｎ－プロピルカルボニルオキシ基、ｎ－ヘキシルカルボニルオキシ基、１－メチル－ｎ－ペンチルカルボニルオキシ基、２－メチル－ｎ－ペンチルカルボニルオキシ基等が挙げられるが、これらに限定されない。
上記ハロゲン基としてはフッ素、塩素、臭素、ヨウ素等が挙げられる。
エポキシ基を有する有機基は例えば、２－（３，４－エポキシシクロヘキシル）エチル基、３－グリシドキシプロピル基等が挙げられる。 Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t -butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2 -dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, etc., but are not limited to these.
The above acyloxy group has 2 to 10 carbon atoms, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butyloxy group. Carbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl -n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl -n-propylcarbonyloxy group, n-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy group, 2-methyl-n-pentylcarbonyloxy group, etc., but are not limited to these.
Examples of the halogen group include fluorine, chlorine, bromine, and iodine.
Examples of the organic group having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyl group and 3-glycidoxypropyl group.
上記アシルオキシ基は炭素原子数２～１０のアシルオキシ基は、例えばメチルカルボニルオキシ基、エチルカルボニルオキシ基、ｎ－プロピルカルボニルオキシ基、ｉ－プロピルカルボニルオキシ基、ｎ－ブチルカルボニルオキシ基、ｉ－ブチルカルボニルオキシ基、ｓ－ブチルカルボニルオキシ基、ｔ－ブチルカルボニルオキシ基、ｎ－ペンチルカルボニルオキシ基、１－メチル－ｎ－ブチルカルボニルオキシ基、２－メチル－ｎ－ブチルカルボニルオキシ基、３－メチル－ｎ－ブチルカルボニルオキシ基、１，１－ジメチル－ｎ－プロピルカルボニルオキシ基、１，２－ジメチル－ｎ－プロピルカルボニルオキシ基、２，２－ジメチル－ｎ－プロピルカルボニルオキシ基、１－エチル－ｎ－プロピルカルボニルオキシ基、ｎ－ヘキシルカルボニルオキシ基、１－メチル－ｎ－ペンチルカルボニルオキシ基、２－メチル－ｎ－ペンチルカルボニルオキシ基等が挙げられるが、これらに限定されない。
上記ハロゲン基としてはフッ素、塩素、臭素、ヨウ素等が挙げられる。
エポキシ基を有する有機基は例えば、２－（３，４－エポキシシクロヘキシル）エチル基、３－グリシドキシプロピル基等が挙げられる。 Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t -butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2 -dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, etc., but are not limited to these.
The above acyloxy group has 2 to 10 carbon atoms, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butyloxy group. Carbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl -n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl -n-propylcarbonyloxy group, n-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy group, 2-methyl-n-pentylcarbonyloxy group, etc., but are not limited to these.
Examples of the halogen group include fluorine, chlorine, bromine, and iodine.
Examples of the organic group having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyl group and 3-glycidoxypropyl group.
上記（メタ）アクリロイル基とは、アクリロイル基とメタクリロイル基の双方をあらわす。（メタ）アクリロイル基を有する有機基は例えば、３－メタクリロキシプロピル基、３－アクリロキシプロピル基等が挙げられる。
メルカプト基を有する有機基は例えば、３－メルカプトプロピル基が挙げられる。
アミノ基を有する有機基は例えば、２－アミノエチル基、３－アミノプロピル基、Ｎ－２－（アミノエチル）－３－アミノプロピル基、Ｎ－（１，３－ジメチル－ブチリデン）アミノプロピル基、Ｎ－フェニル－３－アミノプロピル基、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピル基等が挙げられる。
ウレイド基を有する有機基は例えば、３－ウレイドプロピル基が挙げられる。
シアノ基を有する有機基は例えば、３－シアノプロピル基が挙げられる。
上記式（２）及び式（３）はトリメチルシリル基をシリカ粒子の表面に形成できる化合物が好ましい。 The above (meth)acryloyl group represents both an acryloyl group and a methacryloyl group. Examples of the organic group having a (meth)acryloyl group include a 3-methacryloxypropyl group and a 3-acryloxypropyl group.
An example of the organic group having a mercapto group is a 3-mercaptopropyl group.
Examples of organic groups having an amino group include 2-aminoethyl group, 3-aminopropyl group, N-2-(aminoethyl)-3-aminopropyl group, and N-(1,3-dimethyl-butylidene)aminopropyl group. , N-phenyl-3-aminopropyl group, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group, and the like.
An example of the organic group having a ureido group is a 3-ureidopropyl group.
An example of the organic group having a cyano group is a 3-cyanopropyl group.
The above formulas (2) and (3) are preferably compounds that can form a trimethylsilyl group on the surface of the silica particles.
メルカプト基を有する有機基は例えば、３－メルカプトプロピル基が挙げられる。
アミノ基を有する有機基は例えば、２－アミノエチル基、３－アミノプロピル基、Ｎ－２－（アミノエチル）－３－アミノプロピル基、Ｎ－（１，３－ジメチル－ブチリデン）アミノプロピル基、Ｎ－フェニル－３－アミノプロピル基、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピル基等が挙げられる。
ウレイド基を有する有機基は例えば、３－ウレイドプロピル基が挙げられる。
シアノ基を有する有機基は例えば、３－シアノプロピル基が挙げられる。
上記式（２）及び式（３）はトリメチルシリル基をシリカ粒子の表面に形成できる化合物が好ましい。 The above (meth)acryloyl group represents both an acryloyl group and a methacryloyl group. Examples of the organic group having a (meth)acryloyl group include a 3-methacryloxypropyl group and a 3-acryloxypropyl group.
An example of the organic group having a mercapto group is a 3-mercaptopropyl group.
Examples of organic groups having an amino group include 2-aminoethyl group, 3-aminopropyl group, N-2-(aminoethyl)-3-aminopropyl group, and N-(1,3-dimethyl-butylidene)aminopropyl group. , N-phenyl-3-aminopropyl group, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group, and the like.
An example of the organic group having a ureido group is a 3-ureidopropyl group.
An example of the organic group having a cyano group is a 3-cyanopropyl group.
The above formulas (2) and (3) are preferably compounds that can form a trimethylsilyl group on the surface of the silica particles.
それら化合物としては以下に例示することができる。
上記式中、Ｒ１２はアルコキシ基であり、例えばメトキシ基、エトキシ基が挙げられる。上記シラン化合物は信越化学工業（株）製のシラン化合物を使用する事ができる。
Examples of these compounds are listed below.
In the above formula, R 12 is an alkoxy group, such as a methoxy group or an ethoxy group. As the above-mentioned silane compound, a silane compound manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
シリカ粒子の表面にヒドロキシル基、例えばシリカ粒子であればシラノール基と上記シラン化合物が反応してシロキサン結合によりシリカ粒子の表面に上記シラン化合物を被覆する工程である。反応温度は２０℃からその分散媒の沸点の範囲までの温度で行うことができるが、例えば２０℃～１００℃の範囲で行うことができる。反応時間は０．１～６時間程度で行うことができる。
上記シラン化合物はシリカ粒子表面の被覆量として、シラン化合物中のケイ素原子の個数が０．３個／ｎｍ２～５．０個／ｎｍ２、又は０．６個／ｎｍ２～５．０個／ｎｍ２、又は０．６個／ｎｍ２～３．０個／ｎｍ２の被覆量に相当するシラン化合物をシリカゾルに含有してシリカ粒子表面の被覆を行う事ができる。 This is a step in which the silane compound reacts with a hydroxyl group on the surface of the silica particle, for example, a silanol group in the case of a silica particle, and the surface of the silica particle is coated with the silane compound through a siloxane bond. The reaction temperature can be from 20°C to the boiling point of the dispersion medium, for example from 20°C to 100°C. The reaction time can be about 0.1 to 6 hours.
The number of silicon atoms in the silane compound is 0.3/nm 2 to 5.0/nm 2 or 0.6/nm 2 to 5.0 as the amount of coverage of the silica particle surface of the silane compound. The surface of the silica particles can be coated by containing a silane compound in the silica sol in a coating amount of 0.6/nm 2 or 0.6/nm 2 to 3.0/nm 2 .
上記シラン化合物はシリカ粒子表面の被覆量として、シラン化合物中のケイ素原子の個数が０．３個／ｎｍ２～５．０個／ｎｍ２、又は０．６個／ｎｍ２～５．０個／ｎｍ２、又は０．６個／ｎｍ２～３．０個／ｎｍ２の被覆量に相当するシラン化合物をシリカゾルに含有してシリカ粒子表面の被覆を行う事ができる。 This is a step in which the silane compound reacts with a hydroxyl group on the surface of the silica particle, for example, a silanol group in the case of a silica particle, and the surface of the silica particle is coated with the silane compound through a siloxane bond. The reaction temperature can be from 20°C to the boiling point of the dispersion medium, for example from 20°C to 100°C. The reaction time can be about 0.1 to 6 hours.
The number of silicon atoms in the silane compound is 0.3/nm 2 to 5.0/nm 2 or 0.6/nm 2 to 5.0 as the amount of coverage of the silica particle surface of the silane compound. The surface of the silica particles can be coated by containing a silane compound in the silica sol in a coating amount of 0.6/nm 2 or 0.6/nm 2 to 3.0/nm 2 .
上記シラン化合物の加水分解には水が必要であるが、水性溶媒のゾルであればそれら水性溶媒が用いられる。水性媒体をメタノールやエタノールからなる有機溶媒に溶媒置換した時に溶媒中に残存する水分を用いる事ができる。例えば０．０１～１質量％に存在する水分を用いる事ができる。また、加水分解は触媒を用いて行うことも、触媒なしで行う事もできる。
触媒なしで行う場合はシリカ粒子表面が酸性サイドで存在する場合であり、触媒を用いる場合は、加水分解触媒として金属キレート化合物、有機酸、無機酸、有機塩基、無機塩基を挙げることができる。加水分解触媒としての金属キレート化合物は、例えばトリエトキシ・モノ（アセチルアセトナート）チタン、トリエトキシ・モノ（アセチルアセトナート）ジルコニウム等が挙げられる。加水分解触媒としての有機酸は、例えば酢酸、シュウ酸等が挙げられる。加水分解触媒としての無機酸は、例えば塩酸、硝酸、硫酸、フッ酸、リン酸等が挙げられる。加水分解触媒としての有機塩基は、例えばピリジン、ピロール、ピペラジン、第４級アンモニウム塩が挙げられる。加水分解触媒としての無機塩基としては、例えばアンモニア、水酸化ナトリウム、水酸化カリウムが挙げられる。 Water is required for hydrolysis of the above-mentioned silane compound, and if the sol is an aqueous solvent, such an aqueous solvent can be used. Water remaining in the solvent when the aqueous medium is replaced with an organic solvent such as methanol or ethanol can be used. For example, water present at 0.01 to 1% by weight can be used. Moreover, hydrolysis can be carried out with or without a catalyst.
When carrying out without a catalyst, the silica particle surface is present on the acidic side, and when using a catalyst, examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases. Examples of the metal chelate compound as a hydrolysis catalyst include triethoxy mono(acetylacetonato) titanium and triethoxy mono(acetylacetonato) zirconium. Examples of organic acids as hydrolysis catalysts include acetic acid and oxalic acid. Examples of inorganic acids as hydrolysis catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of organic bases used as hydrolysis catalysts include pyridine, pyrrole, piperazine, and quaternary ammonium salts. Examples of the inorganic base as a hydrolysis catalyst include ammonia, sodium hydroxide, and potassium hydroxide.
触媒なしで行う場合はシリカ粒子表面が酸性サイドで存在する場合であり、触媒を用いる場合は、加水分解触媒として金属キレート化合物、有機酸、無機酸、有機塩基、無機塩基を挙げることができる。加水分解触媒としての金属キレート化合物は、例えばトリエトキシ・モノ（アセチルアセトナート）チタン、トリエトキシ・モノ（アセチルアセトナート）ジルコニウム等が挙げられる。加水分解触媒としての有機酸は、例えば酢酸、シュウ酸等が挙げられる。加水分解触媒としての無機酸は、例えば塩酸、硝酸、硫酸、フッ酸、リン酸等が挙げられる。加水分解触媒としての有機塩基は、例えばピリジン、ピロール、ピペラジン、第４級アンモニウム塩が挙げられる。加水分解触媒としての無機塩基としては、例えばアンモニア、水酸化ナトリウム、水酸化カリウムが挙げられる。 Water is required for hydrolysis of the above-mentioned silane compound, and if the sol is an aqueous solvent, such an aqueous solvent can be used. Water remaining in the solvent when the aqueous medium is replaced with an organic solvent such as methanol or ethanol can be used. For example, water present at 0.01 to 1% by weight can be used. Moreover, hydrolysis can be carried out with or without a catalyst.
When carrying out without a catalyst, the silica particle surface is present on the acidic side, and when using a catalyst, examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases. Examples of the metal chelate compound as a hydrolysis catalyst include triethoxy mono(acetylacetonato) titanium and triethoxy mono(acetylacetonato) zirconium. Examples of organic acids as hydrolysis catalysts include acetic acid and oxalic acid. Examples of inorganic acids as hydrolysis catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of organic bases used as hydrolysis catalysts include pyridine, pyrrole, piperazine, and quaternary ammonium salts. Examples of the inorganic base as a hydrolysis catalyst include ammonia, sodium hydroxide, and potassium hydroxide.
上記シラン化合物が、シリカ粒子と共有結合を介した結合を少なくとも１つ以上含むものである。
本発明ではシリカ粒子が、アルミニウム原子をシリカ粒子表面にＡｌ２Ｏ３に換算して０．００１～２．０質量％／ＳｉＯ２、又は０．００１～１．０質量％／ＳｉＯ２、又は０．００１～０．５質量％／ＳｉＯ２、又は０．００１～０．３質量％／ＳｉＯ２の割合で結合したシリカ粒子とする事ができる。このようにシリカ粒子表面にアルミノシリケートサイトが形成される事により、シリカ粒子表面に存在する負電荷量が増大し、例えば０．２５～０．４０μｅｑ／ｍ２で計測される。
本発明のシリコーン化合物含有有機溶媒シリカゾルは、有機溶媒が窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒を用いる事ができる。
窒素含有溶媒の具体例として、例えばジメチルホルムアミド、ジエチルホルムアミド、ジメチルアセトアミド、ジエチルアセトアミド、Ｎ－メチルピロリドン、Ｎ－エチルピロリドン、テトラメチルウレア、ヘキサメチルホスホリックトリアミド、ジメチルアクリルアミド、アクリロイルモルフォリン、ヒドロキシエチルアクリルアミド、イソプロピルアクリルアミド、ジエチルアクリルアミド、ジメチルアミノプロピルアクリルアミド、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、ジメチルアミノプロピルアクリルアミド塩化メチル４級塩、ジメチルアミノエチルアクリレートベンジルクロライド４級塩等が挙げられる。特に上記窒素含有溶媒がジメチルアセトアミド、ジメチルホルムアミド、Ｎ－メチルピロリドン、又はＮ－エチルピロリドンを用いる事ができる。 The above-mentioned silane compound contains at least one bond via a covalent bond with the silica particle.
In the present invention, the silica particles have aluminum atoms on the surface of the silica particles in an amount of 0.001 to 2.0 mass%/SiO 2 in terms of Al 2 O 3 , or 0.001 to 1.0 mass %/SiO 2 , or The silica particles can be bonded at a ratio of 0.001 to 0.5% by mass/SiO 2 or 0.001 to 0.3% by mass/SiO 2 . By forming aluminosilicate sites on the silica particle surface in this manner, the amount of negative charge present on the silica particle surface increases, and is measured at, for example, 0.25 to 0.40 μeq/m 2 .
In the organic solvent silica sol containing a silicone compound of the present invention, a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent can be used as the organic solvent.
Specific examples of nitrogen-containing solvents include dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, tetramethylurea, hexamethylphosphoric triamide, dimethylacrylamide, acryloylmorpholine, and hydroxyl. Ethylacrylamide, isopropylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, dimethylaminopropylacrylamide methyl chloride quaternary salt, dimethylamino Examples include ethyl acrylate benzyl chloride quaternary salt. In particular, the nitrogen-containing solvent can be dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or N-ethylpyrrolidone.
本発明ではシリカ粒子が、アルミニウム原子をシリカ粒子表面にＡｌ２Ｏ３に換算して０．００１～２．０質量％／ＳｉＯ２、又は０．００１～１．０質量％／ＳｉＯ２、又は０．００１～０．５質量％／ＳｉＯ２、又は０．００１～０．３質量％／ＳｉＯ２の割合で結合したシリカ粒子とする事ができる。このようにシリカ粒子表面にアルミノシリケートサイトが形成される事により、シリカ粒子表面に存在する負電荷量が増大し、例えば０．２５～０．４０μｅｑ／ｍ２で計測される。
本発明のシリコーン化合物含有有機溶媒シリカゾルは、有機溶媒が窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒を用いる事ができる。
窒素含有溶媒の具体例として、例えばジメチルホルムアミド、ジエチルホルムアミド、ジメチルアセトアミド、ジエチルアセトアミド、Ｎ－メチルピロリドン、Ｎ－エチルピロリドン、テトラメチルウレア、ヘキサメチルホスホリックトリアミド、ジメチルアクリルアミド、アクリロイルモルフォリン、ヒドロキシエチルアクリルアミド、イソプロピルアクリルアミド、ジエチルアクリルアミド、ジメチルアミノプロピルアクリルアミド、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、ジメチルアミノプロピルアクリルアミド塩化メチル４級塩、ジメチルアミノエチルアクリレートベンジルクロライド４級塩等が挙げられる。特に上記窒素含有溶媒がジメチルアセトアミド、ジメチルホルムアミド、Ｎ－メチルピロリドン、又はＮ－エチルピロリドンを用いる事ができる。 The above-mentioned silane compound contains at least one bond via a covalent bond with the silica particle.
In the present invention, the silica particles have aluminum atoms on the surface of the silica particles in an amount of 0.001 to 2.0 mass%/SiO 2 in terms of Al 2 O 3 , or 0.001 to 1.0 mass %/SiO 2 , or The silica particles can be bonded at a ratio of 0.001 to 0.5% by mass/SiO 2 or 0.001 to 0.3% by mass/SiO 2 . By forming aluminosilicate sites on the silica particle surface in this manner, the amount of negative charge present on the silica particle surface increases, and is measured at, for example, 0.25 to 0.40 μeq/m 2 .
In the organic solvent silica sol containing a silicone compound of the present invention, a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent can be used as the organic solvent.
Specific examples of nitrogen-containing solvents include dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, tetramethylurea, hexamethylphosphoric triamide, dimethylacrylamide, acryloylmorpholine, and hydroxyl. Ethylacrylamide, isopropylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, dimethylaminopropylacrylamide methyl chloride quaternary salt, dimethylamino Examples include ethyl acrylate benzyl chloride quaternary salt. In particular, the nitrogen-containing solvent can be dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or N-ethylpyrrolidone.
カルボニル基含有酸素含有溶媒としては、ケトン、又はエステルが挙げられる。ケトンは炭素原子数３～３０の直鎖又は環状の脂肪族ケトンであり、例えばメチルエチルケトン、ジエチルケトン、メチルプロピルケトン、メチルイソブチルケトン、ジイソプロピルケトン、ジイソブチルケトン、メチルアミルケトン、シクロヘキサノン等が挙げられる。エステルは炭素原子数２～３０の直鎖又は環状のエステルであり、例えば酢酸エチル、酢酸ｎ－ブチル、酢酸ｓｅｃブチル、酢酸メトキシブチル、酢酸アミル、酢酸ｎ－プロピル、酢酸イソプロピル、乳酸エチル、乳酸ブチル、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、酢酸フェニル、乳酸フェニル、プロピオン酸フェニル等が挙げられる。カルボニル基含有酸素含有溶媒はγブチロラクトン、又はシクロヘキサノンが好ましい。
イオウ含有溶媒としては、ジメチルスルホキシド、又はジメチルスルホンが挙げられる。 Examples of carbonyl group-containing oxygen-containing solvents include ketones and esters. The ketone is a linear or cyclic aliphatic ketone having 3 to 30 carbon atoms, such as methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and the like. Esters are linear or cyclic esters having 2 to 30 carbon atoms, such as ethyl acetate, n-butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, isopropyl acetate, ethyl lactate, lactic acid. Examples include butyl, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, phenyl acetate, phenyl lactate, phenyl propionate, and the like. The carbonyl group-containing oxygen-containing solvent is preferably γ-butyrolactone or cyclohexanone.
Examples of sulfur-containing solvents include dimethyl sulfoxide and dimethyl sulfone.
イオウ含有溶媒としては、ジメチルスルホキシド、又はジメチルスルホンが挙げられる。 Examples of carbonyl group-containing oxygen-containing solvents include ketones and esters. The ketone is a linear or cyclic aliphatic ketone having 3 to 30 carbon atoms, such as methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and the like. Esters are linear or cyclic esters having 2 to 30 carbon atoms, such as ethyl acetate, n-butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, isopropyl acetate, ethyl lactate, lactic acid. Examples include butyl, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, phenyl acetate, phenyl lactate, phenyl propionate, and the like. The carbonyl group-containing oxygen-containing solvent is preferably γ-butyrolactone or cyclohexanone.
Examples of sulfur-containing solvents include dimethyl sulfoxide and dimethyl sulfone.
本発明ではアミンを添加する事ができる。アミンは総炭素原子数が５～３５の第２級アミン及び第３級アミンを例示する事ができる。
上記第２級アミンとしては例えばエチル－ｎ－プロピルアミン、エチルイソプロピルアミン、ジプロピルアミン、ジイソプロピルアミン、エチルブチルアミン、ｎ－プロピルブチルアミン、ジブチルアミン、エチルペンチルアミン、ｎ－プロピルペンチルアミン、イソプロピルペンチルアミン、ジペンチルアミン、エチルオクチルアミン、ｉ－プロピルオクチルアミン、ブチルオクチルアミン、ジオクチルアミン等が挙げられる。
上記第３級アミンとしては例えばトリエチルアミン、エチルジ－ｎ－プロピルアミン、ジエチル－ｎ－プロピルアミン、トリ－ｎ－プロピルアミン、トリイソプロピルアミン、エチルジブチルアミン、ジエチルブチルアミン、イソプロピルジブチルアミン、ジイソプロピルエチルアミン、ジイソプロピルブチルアミン、トリブチルアミン、エチルジペンチルアミン、ジエチルペンチルアミン、トリペンチルアミン、メチルジオクチルアミン、ジメチルオクチルアミン、エチルジオクチルアミン、ジエチルオクチルアミン、トリオクチルアミン、ベンジルジブチルアミン、ジアザビシクロウンデセン等が挙げられる。 In the present invention, amines can be added. Examples of amines include secondary amines and tertiary amines having a total number of carbon atoms of 5 to 35.
Examples of the secondary amines include ethyl-n-propylamine, ethylisopropylamine, dipropylamine, diisopropylamine, ethylbutylamine, n-propylbutylamine, dibutylamine, ethylpentylamine, n-propylpentylamine, and isopropylpentylamine. , dipentylamine, ethyloctylamine, i-propyloctylamine, butyloctylamine, dioctylamine, and the like.
Examples of the above tertiary amines include triethylamine, ethyldi-n-propylamine, diethyl-n-propylamine, tri-n-propylamine, triisopropylamine, ethyldibutylamine, diethylbutylamine, isopropyldibutylamine, diisopropylethylamine, diisopropyl Examples include butylamine, tributylamine, ethyldipentylamine, diethylpentylamine, tripentylamine, methyldioctylamine, dimethyloctylamine, ethyldioctylamine, diethyloctylamine, trioctylamine, benzyldibutylamine, diazabicycloundecene, etc. .
上記第２級アミンとしては例えばエチル－ｎ－プロピルアミン、エチルイソプロピルアミン、ジプロピルアミン、ジイソプロピルアミン、エチルブチルアミン、ｎ－プロピルブチルアミン、ジブチルアミン、エチルペンチルアミン、ｎ－プロピルペンチルアミン、イソプロピルペンチルアミン、ジペンチルアミン、エチルオクチルアミン、ｉ－プロピルオクチルアミン、ブチルオクチルアミン、ジオクチルアミン等が挙げられる。
上記第３級アミンとしては例えばトリエチルアミン、エチルジ－ｎ－プロピルアミン、ジエチル－ｎ－プロピルアミン、トリ－ｎ－プロピルアミン、トリイソプロピルアミン、エチルジブチルアミン、ジエチルブチルアミン、イソプロピルジブチルアミン、ジイソプロピルエチルアミン、ジイソプロピルブチルアミン、トリブチルアミン、エチルジペンチルアミン、ジエチルペンチルアミン、トリペンチルアミン、メチルジオクチルアミン、ジメチルオクチルアミン、エチルジオクチルアミン、ジエチルオクチルアミン、トリオクチルアミン、ベンジルジブチルアミン、ジアザビシクロウンデセン等が挙げられる。 In the present invention, amines can be added. Examples of amines include secondary amines and tertiary amines having a total number of carbon atoms of 5 to 35.
Examples of the secondary amines include ethyl-n-propylamine, ethylisopropylamine, dipropylamine, diisopropylamine, ethylbutylamine, n-propylbutylamine, dibutylamine, ethylpentylamine, n-propylpentylamine, and isopropylpentylamine. , dipentylamine, ethyloctylamine, i-propyloctylamine, butyloctylamine, dioctylamine, and the like.
Examples of the above tertiary amines include triethylamine, ethyldi-n-propylamine, diethyl-n-propylamine, tri-n-propylamine, triisopropylamine, ethyldibutylamine, diethylbutylamine, isopropyldibutylamine, diisopropylethylamine, diisopropyl Examples include butylamine, tributylamine, ethyldipentylamine, diethylpentylamine, tripentylamine, methyldioctylamine, dimethyloctylamine, ethyldioctylamine, diethyloctylamine, trioctylamine, benzyldibutylamine, diazabicycloundecene, etc. .
上記アミンの中でも総炭素原子数が６～３５のアルキル基を有する第２級アミン及び第３級アミンが好ましく、例えばジイソプロピルアミン、トリペンチルアミン、トリイソプロピルアミン、ジメチルオクチルアミン、トリオクチルアミン等が挙げられる。
また、第４級アンモニウムを添加する事ができる。水酸化第４級アンモニウムとしては、総炭素原子数が４～４０の水酸化テトラアルキルアンモニウムが好ましい。例えば水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラｎプロピルアンモニウム、水酸化テトラｉプロピルアンモニウム、水酸化テトラブチルアンモニウム、水酸化エチルトリメチルアンモニウム等が挙げられる。 Among the above amines, secondary amines and tertiary amines having an alkyl group having a total number of carbon atoms of 6 to 35 are preferred, such as diisopropylamine, tripentylamine, triisopropylamine, dimethyloctylamine, trioctylamine, etc. Can be mentioned.
Furthermore, quaternary ammonium can be added. The quaternary ammonium hydroxide is preferably a tetraalkylammonium hydroxide having a total number of carbon atoms of 4 to 40. Examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-i-propylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, and the like.
また、第４級アンモニウムを添加する事ができる。水酸化第４級アンモニウムとしては、総炭素原子数が４～４０の水酸化テトラアルキルアンモニウムが好ましい。例えば水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラｎプロピルアンモニウム、水酸化テトラｉプロピルアンモニウム、水酸化テトラブチルアンモニウム、水酸化エチルトリメチルアンモニウム等が挙げられる。 Among the above amines, secondary amines and tertiary amines having an alkyl group having a total number of carbon atoms of 6 to 35 are preferred, such as diisopropylamine, tripentylamine, triisopropylamine, dimethyloctylamine, trioctylamine, etc. Can be mentioned.
Furthermore, quaternary ammonium can be added. The quaternary ammonium hydroxide is preferably a tetraalkylammonium hydroxide having a total number of carbon atoms of 4 to 40. Examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-i-propylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, and the like.
本発明では上記シリコーン化合物含有有機溶媒シリカゾルと窒素含有ポリマーとを含む組成物を挙げる事ができる。上記組成物は絶縁性組成物を例示する事ができる。
本発明に用いられる窒素含有ポリマーが、ポリイミド、ポリアミド、ポリアミック酸、ポリアミドイミド、ポリエーテルイミド、ポリエステルイミド、又はこれらの混合物を用いる事ができる。
ポリイミドは芳香族ジアミンと芳香族テトラカルボン酸二無水物からポリアミック酸を経由してイミド化して得られるポリマーである。ポリアミック酸を絶縁性樹脂組成物のポリマー成分として利用して、基材に被覆時の加熱によりポリイミドに変換する事もできる。芳香族ジアミンと芳香族テトラカルボン酸二無水物の選択によりポリアミドイミド、ポリエーテルイミド、ポリエステルイミドが選択する事ができる。
上記窒素含有ポリマーの原料となる芳香族ジアミンとしては例えば、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、４，４’－ジアミノジフェニルプロパン、４，４’－ジアミノジフェニルエーテル、ｏ－トリジン、ｏ－ジアニジン、１，５－ジアミノナフタレン、４，４’－ジアミノジフェニルスルフィド、４，４’－ジアミノジフェニルスルホン等が挙げられる。 The present invention includes a composition containing the above-mentioned silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer. The above composition can be exemplified as an insulating composition.
The nitrogen-containing polymer used in the present invention can be polyimide, polyamide, polyamic acid, polyamideimide, polyetherimide, polyesterimide, or a mixture thereof.
Polyimide is a polymer obtained by imidizing aromatic diamine and aromatic tetracarboxylic dianhydride via polyamic acid. Polyamic acid can also be used as a polymer component of an insulating resin composition and converted into polyimide by heating during coating on a substrate. Polyamideimide, polyetherimide, and polyesterimide can be selected by selecting aromatic diamine and aromatic tetracarboxylic dianhydride.
Examples of aromatic diamines that can be used as raw materials for the nitrogen-containing polymer include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, o-tolidine, o-dianidine, Examples include 1,5-diaminonaphthalene, 4,4'-diaminodiphenylsulfide, and 4,4'-diaminodiphenylsulfone.
本発明に用いられる窒素含有ポリマーが、ポリイミド、ポリアミド、ポリアミック酸、ポリアミドイミド、ポリエーテルイミド、ポリエステルイミド、又はこれらの混合物を用いる事ができる。
ポリイミドは芳香族ジアミンと芳香族テトラカルボン酸二無水物からポリアミック酸を経由してイミド化して得られるポリマーである。ポリアミック酸を絶縁性樹脂組成物のポリマー成分として利用して、基材に被覆時の加熱によりポリイミドに変換する事もできる。芳香族ジアミンと芳香族テトラカルボン酸二無水物の選択によりポリアミドイミド、ポリエーテルイミド、ポリエステルイミドが選択する事ができる。
上記窒素含有ポリマーの原料となる芳香族ジアミンとしては例えば、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、４，４’－ジアミノジフェニルプロパン、４，４’－ジアミノジフェニルエーテル、ｏ－トリジン、ｏ－ジアニジン、１，５－ジアミノナフタレン、４，４’－ジアミノジフェニルスルフィド、４，４’－ジアミノジフェニルスルホン等が挙げられる。 The present invention includes a composition containing the above-mentioned silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer. The above composition can be exemplified as an insulating composition.
The nitrogen-containing polymer used in the present invention can be polyimide, polyamide, polyamic acid, polyamideimide, polyetherimide, polyesterimide, or a mixture thereof.
Polyimide is a polymer obtained by imidizing aromatic diamine and aromatic tetracarboxylic dianhydride via polyamic acid. Polyamic acid can also be used as a polymer component of an insulating resin composition and converted into polyimide by heating during coating on a substrate. Polyamideimide, polyetherimide, and polyesterimide can be selected by selecting aromatic diamine and aromatic tetracarboxylic dianhydride.
Examples of aromatic diamines that can be used as raw materials for the nitrogen-containing polymer include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, o-tolidine, o-dianidine, Examples include 1,5-diaminonaphthalene, 4,4'-diaminodiphenylsulfide, and 4,4'-diaminodiphenylsulfone.
上記窒素含有ポリマーの原料となる芳香族テトラカルボン酸二無水物としては例えば、ピロメリット酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物、２，２’－ビス（３，４－ジカルボキシフェノン）プロパン二無水物、ビス（３，４－ジカルボキシフェニル）エーテル二無水物、エチレンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、４，４’－オキシジフタル酸二無水物等が挙げられる。
反応に於ける好ましい溶剤としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、テトラメチレンスルホン、ジメチルスルホン、ピリジン、ジエチレングリコールジメチルエーテル等が挙げられる。溶剤は単独であるいは混合して、又はベンゼン、トルエン、キシレン、ジオキサン、ブチロラクトン、シクロヘキサン等を混合して用いる事ができる。 Examples of the aromatic tetracarboxylic dianhydride used as a raw material for the nitrogen-containing polymer include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenone)propane dianhydride, bis (3,4-dicarboxyphenyl)ether dianhydride, ethylenetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, Examples include 4,4'-oxydiphthalic dianhydride.
Preferred solvents in the reaction include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, tetramethylenesulfone, dimethylsulfone, pyridine, diethylene glycol dimethyl ether, and the like. The solvents can be used alone or in combination, or in combination with benzene, toluene, xylene, dioxane, butyrolactone, cyclohexane, and the like.
反応に於ける好ましい溶剤としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、テトラメチレンスルホン、ジメチルスルホン、ピリジン、ジエチレングリコールジメチルエーテル等が挙げられる。溶剤は単独であるいは混合して、又はベンゼン、トルエン、キシレン、ジオキサン、ブチロラクトン、シクロヘキサン等を混合して用いる事ができる。 Examples of the aromatic tetracarboxylic dianhydride used as a raw material for the nitrogen-containing polymer include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenone)propane dianhydride, bis (3,4-dicarboxyphenyl)ether dianhydride, ethylenetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, Examples include 4,4'-oxydiphthalic dianhydride.
Preferred solvents in the reaction include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, tetramethylenesulfone, dimethylsulfone, pyridine, diethylene glycol dimethyl ether, and the like. The solvents can be used alone or in combination, or in combination with benzene, toluene, xylene, dioxane, butyrolactone, cyclohexane, and the like.
脱水剤としては酢酸、プロピオン酸、イソ酪酸、安息香酸、プロピル安息香酸等の脂肪族及び芳香族カルボン酸無水物が挙げられる。又、イミド化触媒としてはピリジン、イソキノリン、４－メチルピリジン、３－メチルピリジン等の第３級アミンが挙げられる。
上記シリコーン化合物含有有機溶媒シリカゾルは、動的光散乱法（ＤＬＳ法）による平均粒子径が５～１００ｎｍとする事ができる。
上記絶縁性樹脂組成物は窒素含有ポリマーの１質量部に対し、上記シリコーン化合物含有有機溶媒シリカゾルに含まれるシリカ粒子の配合量が０．０１～１質量部にする事ができる。 Examples of dehydrating agents include aliphatic and aromatic carboxylic acid anhydrides such as acetic acid, propionic acid, isobutyric acid, benzoic acid, and propylbenzoic acid. Examples of imidization catalysts include tertiary amines such as pyridine, isoquinoline, 4-methylpyridine, and 3-methylpyridine.
The organic solvent silica sol containing a silicone compound can have an average particle diameter of 5 to 100 nm as measured by dynamic light scattering (DLS).
In the insulating resin composition, the amount of silica particles contained in the silicone compound-containing organic solvent silica sol can be 0.01 to 1 part by mass per 1 part by mass of the nitrogen-containing polymer.
上記シリコーン化合物含有有機溶媒シリカゾルは、動的光散乱法（ＤＬＳ法）による平均粒子径が５～１００ｎｍとする事ができる。
上記絶縁性樹脂組成物は窒素含有ポリマーの１質量部に対し、上記シリコーン化合物含有有機溶媒シリカゾルに含まれるシリカ粒子の配合量が０．０１～１質量部にする事ができる。 Examples of dehydrating agents include aliphatic and aromatic carboxylic acid anhydrides such as acetic acid, propionic acid, isobutyric acid, benzoic acid, and propylbenzoic acid. Examples of imidization catalysts include tertiary amines such as pyridine, isoquinoline, 4-methylpyridine, and 3-methylpyridine.
The organic solvent silica sol containing a silicone compound can have an average particle diameter of 5 to 100 nm as measured by dynamic light scattering (DLS).
In the insulating resin composition, the amount of silica particles contained in the silicone compound-containing organic solvent silica sol can be 0.01 to 1 part by mass per 1 part by mass of the nitrogen-containing polymer.
本発明では上記絶縁性樹脂組成物により導線を絶縁被覆した絶縁被覆導線が得られる。
絶縁性の測定では、シリカ配合量が７～３０質量％有する上記絶縁性樹脂組成物を０．５ｍｍ厚の銅板上に層厚３０～３５μｍで絶縁層を形成し、銅板側に密着した円盤電極（直径２５ｍｍ径）、絶縁層側に密着した球状電極（直径２０ｍｍ径）に対し、印加電圧（交流）３．０ｋＶ、周波数５０Ｈｚ、温度１５５℃とする条件で測定した絶縁寿命が８５分以上、典型的には８５分～２００分の絶縁性が得られる。
本件の有機溶媒シリカゾルは、下記（Ａ）～（Ｃ）工程：
（Ａ）工程：５～１００ｎｍの平均一次粒子径を有するシリカ粒子を含む炭素原子数１～５のアルコール溶媒シリカゾルを準備する工程、
（Ｂ）工程：（Ａ）工程で得られたシリカゾルに式（５）乃至式（７）の何れか１項に記載のシラン化合物を添加し２０～１００℃で０．１～４８時間、又は０．１～６時間の反応を行う工程、
（Ｃ）工程：（Ｂ）工程で得られたシリカゾルを窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒に溶媒置換する工程、を含み製造する事ができる。
上記（Ａ）工程で使用する炭素原子数１～５のアルコールは例えばメタノール、エタノール、ｎ－プロパノール、ｉ－プロパノール、ｎ－ブタノール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等が挙げられる。
（Ｂ）工程開始～（Ｃ）工程終了後までの何れかの段階で第２級又は第３級アミンを添加する工程（Ｄ）を付加する事ができる。 In the present invention, an insulated conductive wire is obtained in which a conductive wire is insulated and coated with the above-mentioned insulating resin composition.
In the measurement of insulation properties, an insulating layer of the above insulating resin composition containing 7 to 30% by mass of silica was formed on a 0.5 mm thick copper plate to a thickness of 30 to 35 μm, and a disk electrode was placed in close contact with the copper plate. (diameter: 25 mm), insulation life is 85 minutes or more when measured under conditions of applied voltage (AC) of 3.0 kV, frequency of 50 Hz, and temperature of 155°C for a spherical electrode (diameter of 20 mm) that is in close contact with the insulating layer side. Typically, insulation for 85 to 200 minutes is obtained.
The organic solvent silica sol of this case is manufactured by the following steps (A) to (C):
(A) Step: preparing an alcohol solvent silica sol having 1 to 5 carbon atoms containing silica particles having an average primary particle diameter of 5 to 100 nm;
(B) Step: A silane compound according to any one of formulas (5) to (7) is added to the silica sol obtained in step (A) at 20 to 100°C for 0.1 to 48 hours, or a step of carrying out a reaction for 0.1 to 6 hours;
(C) Step: Production can include a step of replacing the silica sol obtained in Step (B) with a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent.
Examples of alcohols having 1 to 5 carbon atoms used in the above step (A) include methanol, ethanol, n-propanol, i-propanol, n-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like.
A step (D) of adding a secondary or tertiary amine can be added at any stage from the start of the step (B) to the end of the step (C).
絶縁性の測定では、シリカ配合量が７～３０質量％有する上記絶縁性樹脂組成物を０．５ｍｍ厚の銅板上に層厚３０～３５μｍで絶縁層を形成し、銅板側に密着した円盤電極（直径２５ｍｍ径）、絶縁層側に密着した球状電極（直径２０ｍｍ径）に対し、印加電圧（交流）３．０ｋＶ、周波数５０Ｈｚ、温度１５５℃とする条件で測定した絶縁寿命が８５分以上、典型的には８５分～２００分の絶縁性が得られる。
本件の有機溶媒シリカゾルは、下記（Ａ）～（Ｃ）工程：
（Ａ）工程：５～１００ｎｍの平均一次粒子径を有するシリカ粒子を含む炭素原子数１～５のアルコール溶媒シリカゾルを準備する工程、
（Ｂ）工程：（Ａ）工程で得られたシリカゾルに式（５）乃至式（７）の何れか１項に記載のシラン化合物を添加し２０～１００℃で０．１～４８時間、又は０．１～６時間の反応を行う工程、
（Ｃ）工程：（Ｂ）工程で得られたシリカゾルを窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒に溶媒置換する工程、を含み製造する事ができる。
上記（Ａ）工程で使用する炭素原子数１～５のアルコールは例えばメタノール、エタノール、ｎ－プロパノール、ｉ－プロパノール、ｎ－ブタノール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等が挙げられる。
（Ｂ）工程開始～（Ｃ）工程終了後までの何れかの段階で第２級又は第３級アミンを添加する工程（Ｄ）を付加する事ができる。 In the present invention, an insulated conductive wire is obtained in which a conductive wire is insulated and coated with the above-mentioned insulating resin composition.
In the measurement of insulation properties, an insulating layer of the above insulating resin composition containing 7 to 30% by mass of silica was formed on a 0.5 mm thick copper plate to a thickness of 30 to 35 μm, and a disk electrode was placed in close contact with the copper plate. (diameter: 25 mm), insulation life is 85 minutes or more when measured under conditions of applied voltage (AC) of 3.0 kV, frequency of 50 Hz, and temperature of 155°C for a spherical electrode (diameter of 20 mm) that is in close contact with the insulating layer side. Typically, insulation for 85 to 200 minutes is obtained.
The organic solvent silica sol of this case is manufactured by the following steps (A) to (C):
(A) Step: preparing an alcohol solvent silica sol having 1 to 5 carbon atoms containing silica particles having an average primary particle diameter of 5 to 100 nm;
(B) Step: A silane compound according to any one of formulas (5) to (7) is added to the silica sol obtained in step (A) at 20 to 100°C for 0.1 to 48 hours, or a step of carrying out a reaction for 0.1 to 6 hours;
(C) Step: Production can include a step of replacing the silica sol obtained in Step (B) with a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent.
Examples of alcohols having 1 to 5 carbon atoms used in the above step (A) include methanol, ethanol, n-propanol, i-propanol, n-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like.
A step (D) of adding a secondary or tertiary amine can be added at any stage from the start of the step (B) to the end of the step (C).
本発明の絶縁性樹脂組成物は、上記アルコール溶媒シリカゾル〔有機溶媒シリカゾル（ｉ）〕と、上記窒素含有ポリマー〔窒素含有ポリマー（ｉｉ）〕と、上記式（１）、式（２）、又は式（４）のシリコーン化合物（ｉｉｉ）とを添加し混合する工程（Ｅ）を含み製造する事ができる。
上記有機溶媒シリカゾル（ｉ）と、上記窒素含有ポリマー（ｉｉ）と、上記式（１）、式（２）、又は式（４）のシリコーン化合物（ｉｉｉ）との添加の順序は、少なくとも３者が混合されるのであれば如何なる順序でも可能である。
例えば工程（Ｅ）の添加の順が、
有機溶媒シリカゾル（ｉ）にシリコーン化合物（ｉｉｉ）を添加し更に窒素含有ポリマー（ｉｉ）を添加する工程（Ｅ－１）、
有機溶媒シリカゾル（ｉ）に窒素含有ポリマー（ｉｉ）を添加し更にシリコーン化合物（ｉｉｉ）を添加する工程（Ｅ－２）、又は
窒素含有ポリマー（ｉｉ）にシリコーン化合物（ｉｉｉ）を添加し更に有機溶媒シリカゾル（ｉ）を添加する工程（Ｅ－３）で挙げられた順序で製造する事ができる。
上記絶縁性樹脂組成物は有機溶媒シリカゾルに含まれる有機溶媒を含んでいる事もできるが、組成物中の固形分を上げて塗膜中のシリカ濃度を向上させて形成する事が好ましく、（Ｅ）工程開始～（Ｅ）工程終了後までの何れかの段階でアルコール、窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒等の有機溶媒を除去する（Ｆ）工程を含む事が好ましい。
上記有機溶媒シリカゾル（ｉ）は、式（５）乃至式（７）からなる群より選ばれる少なくとも１種のシラン化合物を含む場合と、含まない場合があるが、式（５）乃至式（７）からなる群より選ばれる少なくとも１種のシラン化合物を含む事が好ましい。 The insulating resin composition of the present invention comprises the alcohol solvent silica sol [organic solvent silica sol (i)], the nitrogen-containing polymer [nitrogen-containing polymer (ii)], and the above formula (1), formula (2), or It can be manufactured by including the step (E) of adding and mixing the silicone compound (iii) of formula (4).
The order of addition of the organic solvent silica sol (i), the nitrogen-containing polymer (ii), and the silicone compound (iii) of the formula (1), formula (2), or formula (4) is at least three. Any order is possible as long as they are mixed.
For example, the order of addition in step (E) is
a step (E-1) of adding a silicone compound (iii) to an organic solvent silica sol (i) and further adding a nitrogen-containing polymer (ii);
Step (E-2) of adding nitrogen-containing polymer (ii) to organic solvent silica sol (i) and then adding silicone compound (iii), or adding silicone compound (iii) to nitrogen-containing polymer (ii) and further adding organic It can be produced in the order listed in the step (E-3) of adding the solvent silica sol (i).
Although the above-mentioned insulating resin composition can contain the organic solvent contained in the organic solvent silica sol, it is preferable to increase the solid content in the composition and improve the silica concentration in the coating film. E) It may include the step (F) of removing an organic solvent such as an alcohol, a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent at any stage from the start of the process to the end of the (E) process. preferable.
The organic solvent silica sol (i) may or may not contain at least one silane compound selected from the group consisting of formulas (5) to (7), and may or may not contain at least one silane compound selected from the group consisting of formulas (5) to (7). ) It is preferable that at least one silane compound selected from the group consisting of:
上記有機溶媒シリカゾル（ｉ）と、上記窒素含有ポリマー（ｉｉ）と、上記式（１）、式（２）、又は式（４）のシリコーン化合物（ｉｉｉ）との添加の順序は、少なくとも３者が混合されるのであれば如何なる順序でも可能である。
例えば工程（Ｅ）の添加の順が、
有機溶媒シリカゾル（ｉ）にシリコーン化合物（ｉｉｉ）を添加し更に窒素含有ポリマー（ｉｉ）を添加する工程（Ｅ－１）、
有機溶媒シリカゾル（ｉ）に窒素含有ポリマー（ｉｉ）を添加し更にシリコーン化合物（ｉｉｉ）を添加する工程（Ｅ－２）、又は
窒素含有ポリマー（ｉｉ）にシリコーン化合物（ｉｉｉ）を添加し更に有機溶媒シリカゾル（ｉ）を添加する工程（Ｅ－３）で挙げられた順序で製造する事ができる。
上記絶縁性樹脂組成物は有機溶媒シリカゾルに含まれる有機溶媒を含んでいる事もできるが、組成物中の固形分を上げて塗膜中のシリカ濃度を向上させて形成する事が好ましく、（Ｅ）工程開始～（Ｅ）工程終了後までの何れかの段階でアルコール、窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒等の有機溶媒を除去する（Ｆ）工程を含む事が好ましい。
上記有機溶媒シリカゾル（ｉ）は、式（５）乃至式（７）からなる群より選ばれる少なくとも１種のシラン化合物を含む場合と、含まない場合があるが、式（５）乃至式（７）からなる群より選ばれる少なくとも１種のシラン化合物を含む事が好ましい。 The insulating resin composition of the present invention comprises the alcohol solvent silica sol [organic solvent silica sol (i)], the nitrogen-containing polymer [nitrogen-containing polymer (ii)], and the above formula (1), formula (2), or It can be manufactured by including the step (E) of adding and mixing the silicone compound (iii) of formula (4).
The order of addition of the organic solvent silica sol (i), the nitrogen-containing polymer (ii), and the silicone compound (iii) of the formula (1), formula (2), or formula (4) is at least three. Any order is possible as long as they are mixed.
For example, the order of addition in step (E) is
a step (E-1) of adding a silicone compound (iii) to an organic solvent silica sol (i) and further adding a nitrogen-containing polymer (ii);
Step (E-2) of adding nitrogen-containing polymer (ii) to organic solvent silica sol (i) and then adding silicone compound (iii), or adding silicone compound (iii) to nitrogen-containing polymer (ii) and further adding organic It can be produced in the order listed in the step (E-3) of adding the solvent silica sol (i).
Although the above-mentioned insulating resin composition can contain the organic solvent contained in the organic solvent silica sol, it is preferable to increase the solid content in the composition and improve the silica concentration in the coating film. E) It may include the step (F) of removing an organic solvent such as an alcohol, a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent at any stage from the start of the process to the end of the (E) process. preferable.
The organic solvent silica sol (i) may or may not contain at least one silane compound selected from the group consisting of formulas (5) to (7), and may or may not contain at least one silane compound selected from the group consisting of formulas (5) to (7). ) It is preferable that at least one silane compound selected from the group consisting of:
（分析方法）
〔ＳｉＯ2濃度の測定〕
シリカゾルを坩堝に取り、１５０℃で乾燥後、得られたゲルを１０００℃にて３０分間焼成し、焼成残分を計量して算出した。
〔平均一次粒子径（窒素吸着法粒子径）の測定〕
シリカゾルの３００℃乾燥粉末の比表面積を比表面積測定装置モノソーブ（商品名）ＭＳ－１６（ユアサアイオニクス（株）製）を用いて測定した。 (Analysis method)
[Measurement of SiO 2 concentration]
The silica sol was placed in a crucible, and after drying at 150°C, the resulting gel was fired at 1000°C for 30 minutes, and the firing residue was measured and calculated.
[Measurement of average primary particle diameter (nitrogen adsorption method particle diameter)]
The specific surface area of the 300° C. dry powder of silica sol was measured using a specific surface area measuring device Monosorb (trade name) MS-16 (manufactured by Yuasa Ionics Co., Ltd.).
〔ＳｉＯ2濃度の測定〕
シリカゾルを坩堝に取り、１５０℃で乾燥後、得られたゲルを１０００℃にて３０分間焼成し、焼成残分を計量して算出した。
〔平均一次粒子径（窒素吸着法粒子径）の測定〕
シリカゾルの３００℃乾燥粉末の比表面積を比表面積測定装置モノソーブ（商品名）ＭＳ－１６（ユアサアイオニクス（株）製）を用いて測定した。 (Analysis method)
[Measurement of SiO 2 concentration]
The silica sol was placed in a crucible, and after drying at 150°C, the resulting gel was fired at 1000°C for 30 minutes, and the firing residue was measured and calculated.
[Measurement of average primary particle diameter (nitrogen adsorption method particle diameter)]
The specific surface area of the 300° C. dry powder of silica sol was measured using a specific surface area measuring device Monosorb (trade name) MS-16 (manufactured by Yuasa Ionics Co., Ltd.).
〔水分の測定〕
カールフィッシャー滴定法にて求めた。
〔ｐＨ測定〕
ｐＨメーター（東亞ディーケーケー（株）製）を用いて測定した。
〔粘度の測定〕
シリカゾルの粘度はオストワルド粘度計を用いて測定した。 [Measurement of moisture]
It was determined by Karl Fischer titration method.
[pH measurement]
It was measured using a pH meter (manufactured by Toa DKK Co., Ltd.).
[Measurement of viscosity]
The viscosity of the silica sol was measured using an Ostwald viscometer.
カールフィッシャー滴定法にて求めた。
〔ｐＨ測定〕
ｐＨメーター（東亞ディーケーケー（株）製）を用いて測定した。
〔粘度の測定〕
シリカゾルの粘度はオストワルド粘度計を用いて測定した。 [Measurement of moisture]
It was determined by Karl Fischer titration method.
[pH measurement]
It was measured using a pH meter (manufactured by Toa DKK Co., Ltd.).
[Measurement of viscosity]
The viscosity of the silica sol was measured using an Ostwald viscometer.
〔動的光散乱法粒子径の測定〕
動的光散乱法粒子径測定装置（マルバーン社製 商品名ゼーターサイザー ナノ）により測定した。
〔全アルミニウム量の測定〕
ＩＣＰ発光分光分析装置（リガク社製 商品名ＣＩＲＯＳ１２０ Ｅ０Ｐ）を使用して金属元素分析を行った。
〔ポリアミック酸の固形分〕
ポリアミック酸をアルミカップに取った後に２００℃にて３時間焼成し、焼成残分を計量して算出した。 [Dynamic light scattering method particle size measurement]
Measurement was performed using a dynamic light scattering particle size measuring device (product name: Zetersizer Nano, manufactured by Malvern).
[Measurement of total aluminum amount]
Metal elemental analysis was performed using an ICP emission spectrometer (manufactured by Rigaku Co., Ltd., trade name CIROS120 E0P).
[Solid content of polyamic acid]
The polyamic acid was placed in an aluminum cup, then baked at 200°C for 3 hours, and the baking residue was weighed to calculate the amount.
動的光散乱法粒子径測定装置（マルバーン社製 商品名ゼーターサイザー ナノ）により測定した。
〔全アルミニウム量の測定〕
ＩＣＰ発光分光分析装置（リガク社製 商品名ＣＩＲＯＳ１２０ Ｅ０Ｐ）を使用して金属元素分析を行った。
〔ポリアミック酸の固形分〕
ポリアミック酸をアルミカップに取った後に２００℃にて３時間焼成し、焼成残分を計量して算出した。 [Dynamic light scattering method particle size measurement]
Measurement was performed using a dynamic light scattering particle size measuring device (product name: Zetersizer Nano, manufactured by Malvern).
[Measurement of total aluminum amount]
Metal elemental analysis was performed using an ICP emission spectrometer (manufactured by Rigaku Co., Ltd., trade name CIROS120 E0P).
[Solid content of polyamic acid]
The polyamic acid was placed in an aluminum cup, then baked at 200°C for 3 hours, and the baking residue was weighed to calculate the amount.
（参考例１）
（ａ）工程：水分散シリカゾル（平均一次粒子径１２ｎｍ、ｐＨ２．５、シリカ濃度２０質量％、Ａｌ２Ｏ３濃度０．４２質量％／ＳｉＯ２、日産化学株式会社製）１０００ｇを撹拌機、コンデンサー、温度計及び注入口２個を備えた内容積２Ｌのガラス製反応器に仕込み、反応器内のゾルを沸騰させたままの状態で、別のボイラーで発生させたメタノールの蒸気を反応器内のシリカゾル中に連続的に吹き込んで、液面を徐々に上昇させながらメタノールによる水の置換を行った。留出液の体積が９Ｌになったところで置換を終了して、メタノール分散シリカゾルを１１００ｇ得た。得られたメタノール分散シリカゾルは、ＳｉＯ２濃度２０.５質量％、水分１．６質量％、粘度２ｍＰａ・ｓであった。
（ｂ）工程：上記メタノールゾルの１０００ｇを２Ｌナスフラスコに仕込み、マグネチックスターラーでゾルを攪拌しながら、フェニルトリメトキシシラン１４．９ｇを添加した後、液温を６０℃で１時間保持した。次に、Ｎ, Ｎ―ジイソプロピルエチルアミン１．６ｇを添加し、その後、メチルエチルケトン１５０ｇを添加し、液温６０℃で５時間保持した。
シラン化合物中のケイ素原子の個数が１．０個／ｎｍ２のシリカ粒子の被覆量に相当するフェニルトリメトキシシランの添加量であった。
（ｃ）工程：その後、ロータリーエバポレーターにて減圧度４５０～１１０Ｔｏｒｒ、浴温度８５～１２５℃で溶媒を蒸発留去させながらＤＭＡＣ（ジメチルアセトアミド）を供給し、ゾルの分散媒をＤＭＡＣに置換することにより、ＤＭＡＣ分散シリカゾル１Ａ（シリカ濃度３０．５質量％、ｐＨ４．６、粘度（２０℃）５ｍＰａ・ｓ、水分０．１質量％、メタノール０．１質量％、動的光散乱法粒子径１８ｎｍ）を得た。 (Reference example 1)
(a) Step: 1000 g of water-dispersed silica sol (average primary particle size 12 nm, pH 2.5, silica concentration 20% by mass, Al2O3 concentration 0.42% by mass/ SiO2 , manufactured by Nissan Chemical Co., Ltd.) was placed in a stirrer, A glass reactor with an internal volume of 2 L equipped with a condenser, a thermometer, and two injection ports is charged, and while the sol in the reactor is kept boiling, methanol vapor generated in another boiler is poured into the reactor. Water was replaced by methanol while the liquid level was gradually raised by continuously blowing into the silica sol in the tank. The substitution was completed when the volume of the distillate reached 9 L, and 1100 g of methanol-dispersed silica sol was obtained. The obtained methanol-dispersed silica sol had an SiO 2 concentration of 20.5% by mass, a water content of 1.6% by mass, and a viscosity of 2 mPa·s.
(b) Step: 1000 g of the above methanol sol was charged into a 2 L eggplant flask, and while stirring the sol with a magnetic stirrer, 14.9 g of phenyltrimethoxysilane was added, and the liquid temperature was maintained at 60° C. for 1 hour. Next, 1.6 g of N,N-diisopropylethylamine was added, followed by 150 g of methyl ethyl ketone, and the liquid temperature was maintained at 60° C. for 5 hours.
The amount of phenyltrimethoxysilane added corresponded to the amount of coating of silica particles in which the number of silicon atoms in the silane compound was 1.0/nm 2 .
(c) Step: Thereafter, DMAC (dimethylacetamide) is supplied while evaporating the solvent using a rotary evaporator at a reduced pressure of 450 to 110 Torr and a bath temperature of 85 to 125°C, and the dispersion medium of the sol is replaced with DMAC. DMAC-dispersed silica sol 1A (silica concentration 30.5% by mass, pH 4.6, viscosity (20°C) 5 mPa・s, water 0.1% by mass, methanol 0.1% by mass, dynamic light scattering particle size 18 nm) ) was obtained.
（ａ）工程：水分散シリカゾル（平均一次粒子径１２ｎｍ、ｐＨ２．５、シリカ濃度２０質量％、Ａｌ２Ｏ３濃度０．４２質量％／ＳｉＯ２、日産化学株式会社製）１０００ｇを撹拌機、コンデンサー、温度計及び注入口２個を備えた内容積２Ｌのガラス製反応器に仕込み、反応器内のゾルを沸騰させたままの状態で、別のボイラーで発生させたメタノールの蒸気を反応器内のシリカゾル中に連続的に吹き込んで、液面を徐々に上昇させながらメタノールによる水の置換を行った。留出液の体積が９Ｌになったところで置換を終了して、メタノール分散シリカゾルを１１００ｇ得た。得られたメタノール分散シリカゾルは、ＳｉＯ２濃度２０.５質量％、水分１．６質量％、粘度２ｍＰａ・ｓであった。
（ｂ）工程：上記メタノールゾルの１０００ｇを２Ｌナスフラスコに仕込み、マグネチックスターラーでゾルを攪拌しながら、フェニルトリメトキシシラン１４．９ｇを添加した後、液温を６０℃で１時間保持した。次に、Ｎ, Ｎ―ジイソプロピルエチルアミン１．６ｇを添加し、その後、メチルエチルケトン１５０ｇを添加し、液温６０℃で５時間保持した。
シラン化合物中のケイ素原子の個数が１．０個／ｎｍ２のシリカ粒子の被覆量に相当するフェニルトリメトキシシランの添加量であった。
（ｃ）工程：その後、ロータリーエバポレーターにて減圧度４５０～１１０Ｔｏｒｒ、浴温度８５～１２５℃で溶媒を蒸発留去させながらＤＭＡＣ（ジメチルアセトアミド）を供給し、ゾルの分散媒をＤＭＡＣに置換することにより、ＤＭＡＣ分散シリカゾル１Ａ（シリカ濃度３０．５質量％、ｐＨ４．６、粘度（２０℃）５ｍＰａ・ｓ、水分０．１質量％、メタノール０．１質量％、動的光散乱法粒子径１８ｎｍ）を得た。 (Reference example 1)
(a) Step: 1000 g of water-dispersed silica sol (average primary particle size 12 nm, pH 2.5, silica concentration 20% by mass, Al2O3 concentration 0.42% by mass/ SiO2 , manufactured by Nissan Chemical Co., Ltd.) was placed in a stirrer, A glass reactor with an internal volume of 2 L equipped with a condenser, a thermometer, and two injection ports is charged, and while the sol in the reactor is kept boiling, methanol vapor generated in another boiler is poured into the reactor. Water was replaced by methanol while the liquid level was gradually raised by continuously blowing into the silica sol in the tank. The substitution was completed when the volume of the distillate reached 9 L, and 1100 g of methanol-dispersed silica sol was obtained. The obtained methanol-dispersed silica sol had an SiO 2 concentration of 20.5% by mass, a water content of 1.6% by mass, and a viscosity of 2 mPa·s.
(b) Step: 1000 g of the above methanol sol was charged into a 2 L eggplant flask, and while stirring the sol with a magnetic stirrer, 14.9 g of phenyltrimethoxysilane was added, and the liquid temperature was maintained at 60° C. for 1 hour. Next, 1.6 g of N,N-diisopropylethylamine was added, followed by 150 g of methyl ethyl ketone, and the liquid temperature was maintained at 60° C. for 5 hours.
The amount of phenyltrimethoxysilane added corresponded to the amount of coating of silica particles in which the number of silicon atoms in the silane compound was 1.0/nm 2 .
(c) Step: Thereafter, DMAC (dimethylacetamide) is supplied while evaporating the solvent using a rotary evaporator at a reduced pressure of 450 to 110 Torr and a bath temperature of 85 to 125°C, and the dispersion medium of the sol is replaced with DMAC. DMAC-dispersed silica sol 1A (silica concentration 30.5% by mass, pH 4.6, viscosity (20°C) 5 mPa・s, water 0.1% by mass, methanol 0.1% by mass, dynamic light scattering particle size 18 nm) ) was obtained.
（参考例２）
参考例１の（ｂ）工程と同様の手法で、参考例１（ａ）工程のメタノールゾルの１０００ｇを２Ｌナスフラスコに仕込み、マグネチックスターラーゾルでゾルを攪拌しながら、メチルトリメトキシシラン（信越化学工業（株）製、商品名ＫＢＭ－１３）１０．３ｇを添加した後、液温を６０℃で１時間保持した。シラン化合物中のケイ素原子の個数が１．０個／ｎｍ２のシリカ粒子の被覆量に相当するメチルトリメトキシシランの添加量であった。
次に、Ｎ, Ｎ―ジイソプロピルエチルアミン１．６gを添加し、その後、メチルエチルケトン１５０ｇを添加し、液温６０℃で５時間保持した。
次いで、参考例１の（ｃ）工程と同様の手法にて溶媒置換を行うことで、ＤＭＡＣ分散シリカゾル２Ａ（シリカ濃度３０．５質量％、ｐＨ４．４、粘度（２０℃）５ｍＰａ・ｓ、水分０．１質量％、メタノール０．１質量％、動的光散乱法粒子径２１ｎｍ） (Reference example 2)
Using the same method as in step (b) of Reference Example 1, 1000 g of the methanol sol in step (a) of Reference Example 1 was charged into a 2L eggplant flask, and while stirring the sol with a magnetic stirrer sol, methyltrimethoxysilane (Shin-Etsu After adding 10.3 g of KBM-13 (trade name, manufactured by Kagaku Kogyo Co., Ltd.), the liquid temperature was maintained at 60° C. for 1 hour. The amount of methyltrimethoxysilane added corresponded to the amount of coating of silica particles in which the number of silicon atoms in the silane compound was 1.0/nm 2 .
Next, 1.6 g of N,N-diisopropylethylamine was added, followed by 150 g of methyl ethyl ketone, and the liquid temperature was maintained at 60° C. for 5 hours.
Next, by performing solvent replacement in the same manner as in step (c) of Reference Example 1, DMAC-dispersed silica sol 2A (silica concentration 30.5% by mass, pH 4.4, viscosity (20°C) 5 mPa・s, moisture 0.1% by mass, methanol 0.1% by mass, dynamic light scattering particle size 21nm)
参考例１の（ｂ）工程と同様の手法で、参考例１（ａ）工程のメタノールゾルの１０００ｇを２Ｌナスフラスコに仕込み、マグネチックスターラーゾルでゾルを攪拌しながら、メチルトリメトキシシラン（信越化学工業（株）製、商品名ＫＢＭ－１３）１０．３ｇを添加した後、液温を６０℃で１時間保持した。シラン化合物中のケイ素原子の個数が１．０個／ｎｍ２のシリカ粒子の被覆量に相当するメチルトリメトキシシランの添加量であった。
次に、Ｎ, Ｎ―ジイソプロピルエチルアミン１．６gを添加し、その後、メチルエチルケトン１５０ｇを添加し、液温６０℃で５時間保持した。
次いで、参考例１の（ｃ）工程と同様の手法にて溶媒置換を行うことで、ＤＭＡＣ分散シリカゾル２Ａ（シリカ濃度３０．５質量％、ｐＨ４．４、粘度（２０℃）５ｍＰａ・ｓ、水分０．１質量％、メタノール０．１質量％、動的光散乱法粒子径２１ｎｍ） (Reference example 2)
Using the same method as in step (b) of Reference Example 1, 1000 g of the methanol sol in step (a) of Reference Example 1 was charged into a 2L eggplant flask, and while stirring the sol with a magnetic stirrer sol, methyltrimethoxysilane (Shin-Etsu After adding 10.3 g of KBM-13 (trade name, manufactured by Kagaku Kogyo Co., Ltd.), the liquid temperature was maintained at 60° C. for 1 hour. The amount of methyltrimethoxysilane added corresponded to the amount of coating of silica particles in which the number of silicon atoms in the silane compound was 1.0/nm 2 .
Next, 1.6 g of N,N-diisopropylethylamine was added, followed by 150 g of methyl ethyl ketone, and the liquid temperature was maintained at 60° C. for 5 hours.
Next, by performing solvent replacement in the same manner as in step (c) of Reference Example 1, DMAC-dispersed silica sol 2A (silica concentration 30.5% by mass, pH 4.4, viscosity (20°C) 5 mPa・s, moisture 0.1% by mass, methanol 0.1% by mass, dynamic light scattering particle size 21nm)
（参考例３）
参考例１の（ｃ）工程と同様の手法で、（ａ）工程のメタノールゾルの１０００ｇを２Ｌナスフラスコに仕込み、ロータリーエバポレーターにて減圧度４５０～１１０Ｔｏｒｒ、浴温度８５～１２５℃で溶媒を蒸発留去させながらＤＭＡＣ（ジメチルアセトアミド）を供給し、ゾルの分散媒をＤＭＡＣに置換することにより、ＤＭＡＣ分散シリカゾル３Ａ（シリカ濃度２０．８質量％、ｐＨ４．０、粘度（２０℃）２ｍＰａ・ｓ、水分０．２質量％、メタノール０．４質量％、動的光散乱法粒子径２１ｎｍ）を得た。 (Reference example 3)
Using the same method as in step (c) of Reference Example 1, 1000 g of the methanol sol in step (a) was placed in a 2 L eggplant flask, and the solvent was evaporated using a rotary evaporator at a reduced pressure of 450 to 110 Torr and a bath temperature of 85 to 125°C. By supplying DMAC (dimethylacetamide) while distilling it off and replacing the dispersion medium of the sol with DMAC, DMAC-dispersed silica sol 3A (silica concentration 20.8% by mass, pH 4.0, viscosity (20°C) 2 mPa・s) , 0.2% by mass of water, 0.4% by mass of methanol, and a dynamic light scattering particle size of 21 nm).
参考例１の（ｃ）工程と同様の手法で、（ａ）工程のメタノールゾルの１０００ｇを２Ｌナスフラスコに仕込み、ロータリーエバポレーターにて減圧度４５０～１１０Ｔｏｒｒ、浴温度８５～１２５℃で溶媒を蒸発留去させながらＤＭＡＣ（ジメチルアセトアミド）を供給し、ゾルの分散媒をＤＭＡＣに置換することにより、ＤＭＡＣ分散シリカゾル３Ａ（シリカ濃度２０．８質量％、ｐＨ４．０、粘度（２０℃）２ｍＰａ・ｓ、水分０．２質量％、メタノール０．４質量％、動的光散乱法粒子径２１ｎｍ）を得た。 (Reference example 3)
Using the same method as in step (c) of Reference Example 1, 1000 g of the methanol sol in step (a) was placed in a 2 L eggplant flask, and the solvent was evaporated using a rotary evaporator at a reduced pressure of 450 to 110 Torr and a bath temperature of 85 to 125°C. By supplying DMAC (dimethylacetamide) while distilling it off and replacing the dispersion medium of the sol with DMAC, DMAC-dispersed silica sol 3A (silica concentration 20.8% by mass, pH 4.0, viscosity (20°C) 2 mPa・s) , 0.2% by mass of water, 0.4% by mass of methanol, and a dynamic light scattering particle size of 21 nm).
（参考例４）
水分散シリカゾル（平均一次粒子径１２ｎｍ、ｐＨ３、シリカ濃度３３質量％、Ａｌ２Ｏ３濃度０．２３質量％／ＳｉＯ２、日産化学株式会社製）を用い、参考例１の（ｂ）工程と同様の手法で溶媒置換を行うことでメタノール分散シリカゾル（シリカ濃度３０．５質量％、ｐＨ４．２、水分０．５質量％、粘度２ｍＰａ・ｓ）を得た。
上記メタノールゾルの１０００ｇを２Ｌナスフラスコに仕込み、ロータリーエバポレーターにて減圧度４５０～１１０Ｔｏｒｒ、浴温度８５～１２５℃で溶媒を蒸発留去させながらＤＭＡＣ（ジメチルアセトアミド）を供給し、ゾルの分散媒をＤＭＡＣに置換することにより、ＤＭＡＣ分散シリカゾル４Ａ（シリカ濃度２０．５質量％、ｐＨ４．９、粘度（２０℃）３ｍＰａ・ｓ、水分０．２質量％、メタノール０．６質量％、動的光散乱法粒子径１８ｎｍ）を得た。 (Reference example 4)
Step (b) of Reference Example 1 and A methanol-dispersed silica sol (silica concentration: 30.5% by mass, pH: 4.2, moisture: 0.5% by mass, viscosity: 2 mPa·s) was obtained by replacing the solvent in a similar manner.
1,000 g of the above methanol sol was placed in a 2L eggplant flask, and DMAC (dimethylacetamide) was supplied while the solvent was evaporated off using a rotary evaporator at a reduced pressure of 450 to 110 Torr and a bath temperature of 85 to 125°C. By replacing DMAC with DMAC, DMAC-dispersed silica sol 4A (silica concentration 20.5% by mass, pH 4.9, viscosity (20°C) 3 mPa・s, water 0.2% by mass, methanol 0.6% by mass, dynamic light A particle size of 18 nm by scattering method was obtained.
水分散シリカゾル（平均一次粒子径１２ｎｍ、ｐＨ３、シリカ濃度３３質量％、Ａｌ２Ｏ３濃度０．２３質量％／ＳｉＯ２、日産化学株式会社製）を用い、参考例１の（ｂ）工程と同様の手法で溶媒置換を行うことでメタノール分散シリカゾル（シリカ濃度３０．５質量％、ｐＨ４．２、水分０．５質量％、粘度２ｍＰａ・ｓ）を得た。
上記メタノールゾルの１０００ｇを２Ｌナスフラスコに仕込み、ロータリーエバポレーターにて減圧度４５０～１１０Ｔｏｒｒ、浴温度８５～１２５℃で溶媒を蒸発留去させながらＤＭＡＣ（ジメチルアセトアミド）を供給し、ゾルの分散媒をＤＭＡＣに置換することにより、ＤＭＡＣ分散シリカゾル４Ａ（シリカ濃度２０．５質量％、ｐＨ４．９、粘度（２０℃）３ｍＰａ・ｓ、水分０．２質量％、メタノール０．６質量％、動的光散乱法粒子径１８ｎｍ）を得た。 (Reference example 4)
Step (b) of Reference Example 1 and A methanol-dispersed silica sol (silica concentration: 30.5% by mass, pH: 4.2, moisture: 0.5% by mass, viscosity: 2 mPa·s) was obtained by replacing the solvent in a similar manner.
1,000 g of the above methanol sol was placed in a 2L eggplant flask, and DMAC (dimethylacetamide) was supplied while the solvent was evaporated off using a rotary evaporator at a reduced pressure of 450 to 110 Torr and a bath temperature of 85 to 125°C. By replacing DMAC with DMAC, DMAC-dispersed silica sol 4A (silica concentration 20.5% by mass, pH 4.9, viscosity (20°C) 3 mPa・s, water 0.2% by mass, methanol 0.6% by mass, dynamic light A particle size of 18 nm by scattering method was obtained.
（参考例５）
４，４’－ジアミノジフェニルエーテル(ＤＤＥ)、及びピロメリット酸二無水物（ＰＭＤＡ）、溶剤としてＮＭＰ（Ｎ－メチルピロリドン)及びＤＭＡＣ(ジメチルアセトアミド)を用い攪拌下５０℃の温度で重合し、式（８）に相当するポリアミック酸（固形分１７％、Ｅ型粘度計で２５℃の粘度が１３６４０ｍＰａ・ｓ）を得た。ポリアミック酸の重合は上記ＤＤＥとＰＭＤＡは１：１の等モルで重合させた。得られたポリアミック酸の重量平均分子量は６３０００であった。式（８）中のｎは繰り返し単位の数である。
(Reference example 5)
4,4'-diaminodiphenyl ether (DDE) and pyromellitic dianhydride (PMDA) were polymerized at a temperature of 50°C with stirring using NMP (N-methylpyrrolidone) and DMAC (dimethylacetamide) as solvents, and the formula A polyamic acid corresponding to (8) (solid content 17%, viscosity at 25°C measured by an E-type viscometer was 13640 mPa·s) was obtained. Polyamic acid was polymerized by using the above DDE and PMDA in an equimolar ratio of 1:1. The weight average molecular weight of the obtained polyamic acid was 63,000. n in formula (8) is the number of repeating units.
４，４’－ジアミノジフェニルエーテル(ＤＤＥ)、及びピロメリット酸二無水物（ＰＭＤＡ）、溶剤としてＮＭＰ（Ｎ－メチルピロリドン)及びＤＭＡＣ(ジメチルアセトアミド)を用い攪拌下５０℃の温度で重合し、式（８）に相当するポリアミック酸（固形分１７％、Ｅ型粘度計で２５℃の粘度が１３６４０ｍＰａ・ｓ）を得た。ポリアミック酸の重合は上記ＤＤＥとＰＭＤＡは１：１の等モルで重合させた。得られたポリアミック酸の重量平均分子量は６３０００であった。式（８）中のｎは繰り返し単位の数である。
4,4'-diaminodiphenyl ether (DDE) and pyromellitic dianhydride (PMDA) were polymerized at a temperature of 50°C with stirring using NMP (N-methylpyrrolidone) and DMAC (dimethylacetamide) as solvents, and the formula A polyamic acid corresponding to (8) (solid content 17%, viscosity at 25°C measured by an E-type viscometer was 13640 mPa·s) was obtained. Polyamic acid was polymerized by using the above DDE and PMDA in an equimolar ratio of 1:1. The weight average molecular weight of the obtained polyamic acid was 63,000. n in formula (8) is the number of repeating units.
（実施例１）
参考例１で得られたＤＭＡＣ分散シリカゾル１Ａの１００ｇにシリコーン化合物成分としてエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４０、一般式（１）においてアルコキシ基としてエトキシ基、平均分子量は７４５、平均して５量体であった。なお、エチルシリケート４０は、ＳｉＯ２をも含む。）０．９０ｇを添加した。手で１０回程度強く振とうした後、ミックスローター（アズワン（株）社製、商品名ＭＲ－５）を用いて２３℃で１時間混合し、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２２ｎｍ、ＳｉＯ2濃度３０．８質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が２．８質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が２．７質量％であった。
次いで、上記ゾルを参考例５で得られたポリアミック酸に樹脂／ＳｉＯ２＝８０／２０になるようにガラス瓶中で添加混合し、真空脱泡機（ＥＭＥ社製、商品名Ｖ－ｍｉｎｉ３００）で２０分間脱泡攪拌することで、シリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 1)
To 100 g of DMAC-dispersed silica sol 1A obtained in Reference Example 1, ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name ethyl silicate 40, ethoxy group as the alkoxy group in general formula (1), average molecular weight 745) was added as a silicone compound component. , was a pentamer on average. Note that ethyl silicate 40 also includes SiO 2 ) 0.90 g was added. After shaking vigorously by hand about 10 times, the mixture was mixed for 1 hour at 23°C using a mix rotor (manufactured by As One Co., Ltd., trade name MR-5). A particle size of 22 nm and a SiO 2 concentration of 30.8% by mass were obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 2.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 2.7% by mass.
Next, the above sol was added to the polyamic acid obtained in Reference Example 5 and mixed in a glass bottle so that the resin/SiO 2 ratio was 80/20, and the mixture was mixed with a vacuum defoaming machine (manufactured by EME, trade name: V-mini 300). By defoaming and stirring for 20 minutes, a silica-containing polyamic acid (insulating resin composition) was obtained.
参考例１で得られたＤＭＡＣ分散シリカゾル１Ａの１００ｇにシリコーン化合物成分としてエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４０、一般式（１）においてアルコキシ基としてエトキシ基、平均分子量は７４５、平均して５量体であった。なお、エチルシリケート４０は、ＳｉＯ２をも含む。）０．９０ｇを添加した。手で１０回程度強く振とうした後、ミックスローター（アズワン（株）社製、商品名ＭＲ－５）を用いて２３℃で１時間混合し、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２２ｎｍ、ＳｉＯ2濃度３０．８質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が２．８質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が２．７質量％であった。
次いで、上記ゾルを参考例５で得られたポリアミック酸に樹脂／ＳｉＯ２＝８０／２０になるようにガラス瓶中で添加混合し、真空脱泡機（ＥＭＥ社製、商品名Ｖ－ｍｉｎｉ３００）で２０分間脱泡攪拌することで、シリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 1)
To 100 g of DMAC-dispersed silica sol 1A obtained in Reference Example 1, ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name ethyl silicate 40, ethoxy group as the alkoxy group in general formula (1), average molecular weight 745) was added as a silicone compound component. , was a pentamer on average. Note that ethyl silicate 40 also includes SiO 2 ) 0.90 g was added. After shaking vigorously by hand about 10 times, the mixture was mixed for 1 hour at 23°C using a mix rotor (manufactured by As One Co., Ltd., trade name MR-5). A particle size of 22 nm and a SiO 2 concentration of 30.8% by mass were obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 2.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 2.7% by mass.
Next, the above sol was added to the polyamic acid obtained in Reference Example 5 and mixed in a glass bottle so that the resin/SiO 2 ratio was 80/20, and the mixture was mixed with a vacuum defoaming machine (manufactured by EME, trade name: V-mini 300). By defoaming and stirring for 20 minutes, a silica-containing polyamic acid (insulating resin composition) was obtained.
（実施例２）
実施例１のエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４０）の添加量を１．７ｇに変更した以外は実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３０．８質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５．６質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が５．５質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 2)
The same procedure as in Example 1 was carried out except that the amount of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: ethyl silicate 40) was changed to 1.7 g. A particle size of 21 nm as determined by light scattering method and a SiO 2 concentration of 30.8% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 5.6% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 5.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
実施例１のエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４０）の添加量を１．７ｇに変更した以外は実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３０．８質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５．６質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が５．５質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 2)
The same procedure as in Example 1 was carried out except that the amount of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: ethyl silicate 40) was changed to 1.7 g. A particle size of 21 nm as determined by light scattering method and a SiO 2 concentration of 30.8% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 5.6% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 5.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
（実施例３）
実施例１のエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４０）の添加量を４．３ｇに変更した以外は実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２５ｎｍ、ＳｉＯ2濃度３０．４質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が１４．０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が１３．５質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 3)
The same procedure as in Example 1 was carried out except that the amount of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethyl silicate 40) was changed to 4.3 g. A particle size of 25 nm as determined by light scattering method and a SiO 2 concentration of 30.4% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 14.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 13.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
実施例１のエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４０）の添加量を４．３ｇに変更した以外は実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２５ｎｍ、ＳｉＯ2濃度３０．４質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が１４．０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が１３．５質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 3)
The same procedure as in Example 1 was carried out except that the amount of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethyl silicate 40) was changed to 4.3 g. A particle size of 25 nm as determined by light scattering method and a SiO 2 concentration of 30.4% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 14.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 13.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
（実施例４）
実施例１のエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４０）の添加量を１７．１ｇに変更した以外は実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２０ｎｍ、ＳｉＯ2濃度３１．４質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５６．０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が４６．５質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 4)
The same procedure as in Example 1 was carried out except that the amount of ethylsilicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethylsilicate 40) was changed to 17.1 g. A particle size of 20 nm as determined by optical scattering method and a SiO 2 concentration of 31.4% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 56.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 46.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
実施例１のエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４０）の添加量を１７．１ｇに変更した以外は実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２０ｎｍ、ＳｉＯ2濃度３１．４質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５６．０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が４６．５質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 4)
The same procedure as in Example 1 was carried out except that the amount of ethylsilicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethylsilicate 40) was changed to 17.1 g. A particle size of 20 nm as determined by optical scattering method and a SiO 2 concentration of 31.4% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 56.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 46.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
（実施例５）
実施例１のシリコーン化合物成分をエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４８、一般式（１）においてアルコキシ基としてエトキシ基、平均分子量は１４００、平均して１０量体であった。）１．６ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２０ｎｍ、ＳｉＯ2濃度３０．３質量％）を得た。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５．３質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が５．３質量％であった。 (Example 5)
The silicone compound component of Example 1 was an ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name ethyl silicate 48, in the general formula (1), the alkoxy group was an ethoxy group, the average molecular weight was 1400, and the average was a decamer. ) Except that the amount was changed to 1.6 g, the same operation as in Example 1 was performed to obtain a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 20 nm, SiO 2 concentration: 30.3% by mass). Next, in the same manner as in Example 1, the mixture was mixed with polyamic acid to obtain a silica-containing polyamic acid. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 5.3% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 5.3% by mass.
実施例１のシリコーン化合物成分をエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４８、一般式（１）においてアルコキシ基としてエトキシ基、平均分子量は１４００、平均して１０量体であった。）１．６ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２０ｎｍ、ＳｉＯ2濃度３０．３質量％）を得た。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５．３質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が５．３質量％であった。 (Example 5)
The silicone compound component of Example 1 was an ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name ethyl silicate 48, in the general formula (1), the alkoxy group was an ethoxy group, the average molecular weight was 1400, and the average was a decamer. ) Except that the amount was changed to 1.6 g, the same operation as in Example 1 was performed to obtain a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 20 nm, SiO 2 concentration: 30.3% by mass). Next, in the same manner as in Example 1, the mixture was mixed with polyamic acid to obtain a silica-containing polyamic acid. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 5.3% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 5.3% by mass.
（実施例６）
実施例１のシリコーン化合物成分をエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４８）３．３ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２０ｎｍ、ＳｉＯ2濃度３０．３質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が１０．７質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が１０．４質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 6)
The same procedure as in Example 1 was carried out except that the silicone compound component in Example 1 was changed to 3.3 g of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethyl Silicate 48), and a silicone compound-containing organic solvent silica sol ( A dynamic light scattering method particle size of 20 nm and SiO 2 concentration of 30.3% by mass) were obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 10.7% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 10.4% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
実施例１のシリコーン化合物成分をエチルシリケートオリゴマー（コルコート（株）製、商品名エチルシリケート４８）３．３ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２０ｎｍ、ＳｉＯ2濃度３０．３質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が１０．７質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が１０．４質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 6)
The same procedure as in Example 1 was carried out except that the silicone compound component in Example 1 was changed to 3.3 g of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethyl Silicate 48), and a silicone compound-containing organic solvent silica sol ( A dynamic light scattering method particle size of 20 nm and SiO 2 concentration of 30.3% by mass) were obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 10.7% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 10.4% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
（実施例７）
実施例１のシリコーン化合物成分をシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－２１３、一般式（２）においてアルコキシ基としてメトキシ基、有機官能基としてフェニル基とメチル基を有し、動粘度（２５℃）１６ｍｍ２／ｓ）１７．２ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３０．１質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５６．５質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が４８．８質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 7)
The silicone compound component of Example 1 was converted into a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-213, having a methoxy group as an alkoxy group and a phenyl group and a methyl group as organic functional groups in the general formula (2), The operation was carried out in the same manner as in Example 1, except that the kinematic viscosity (25° C.) was changed to 16 mm 2 /s ) 17.2 g. .1% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 56.5% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 48.8% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
実施例１のシリコーン化合物成分をシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－２１３、一般式（２）においてアルコキシ基としてメトキシ基、有機官能基としてフェニル基とメチル基を有し、動粘度（２５℃）１６ｍｍ２／ｓ）１７．２ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３０．１質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５６．５質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が４８．８質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 7)
The silicone compound component of Example 1 was converted into a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-213, having a methoxy group as an alkoxy group and a phenyl group and a methyl group as organic functional groups in the general formula (2), The operation was carried out in the same manner as in Example 1, except that the kinematic viscosity (25° C.) was changed to 16 mm 2 /s ) 17.2 g. .1% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 56.5% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 48.8% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
（実施例８）
実施例１のシリコーン化合物成分をシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＣ－８９Ｓ、一般式（２）においてアルコキシ基としてメトキシ基、有機官能基としてメチル基を有し、動粘度（２５℃）５ｍｍ２／ｓ）１６．１ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３３．０質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５２．７質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が４２．０質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 8)
The silicone compound component of Example 1 was a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KC-89S, having a methoxy group as an alkoxy group and a methyl group as an organic functional group in the general formula (2), and having a kinematic viscosity ( 25°C) 5 mm 2 /s) 16.1 g, the same operation as in Example 1 was carried out, and a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 21 nm, SiO 2 concentration 33.0 mass) %) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 52.7% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 42.0% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
実施例１のシリコーン化合物成分をシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＣ－８９Ｓ、一般式（２）においてアルコキシ基としてメトキシ基、有機官能基としてメチル基を有し、動粘度（２５℃）５ｍｍ２／ｓ）１６．１ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３３．０質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５２．７質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が４２．０質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 8)
The silicone compound component of Example 1 was a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KC-89S, having a methoxy group as an alkoxy group and a methyl group as an organic functional group in the general formula (2), and having a kinematic viscosity ( 25°C) 5 mm 2 /s) 16.1 g, the same operation as in Example 1 was carried out, and a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 21 nm, SiO 2 concentration 33.0 mass) %) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 52.7% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 42.0% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
（実施例９）
実施例１のシリコーン化合物成分をシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－５１５、一般式（２）においてアルコキシ基としてメトキシ基、有機官能基としてメチル基を有し、動粘度（２５℃）７ｍｍ２／ｓ）２．１ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３０．１質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が６．８質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が６．７質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 9)
The silicone compound component of Example 1 was a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515, having a methoxy group as an alkoxy group and a methyl group as an organic functional group in the general formula (2), and having a kinematic viscosity ( 25° C.) 7 mm 2 /s) 2.1 g, the same operation was carried out as in Example 1, and a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 21 nm, SiO 2 concentration 30.1 mass) %) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 6.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.7% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
実施例１のシリコーン化合物成分をシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－５１５、一般式（２）においてアルコキシ基としてメトキシ基、有機官能基としてメチル基を有し、動粘度（２５℃）７ｍｍ２／ｓ）２．１ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３０．１質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が６．８質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が６．７質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 9)
The silicone compound component of Example 1 was a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515, having a methoxy group as an alkoxy group and a methyl group as an organic functional group in the general formula (2), and having a kinematic viscosity ( 25° C.) 7 mm 2 /s) 2.1 g, the same operation was carried out as in Example 1, and a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 21 nm, SiO 2 concentration 30.1 mass) %) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 6.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.7% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
（実施例１０）
実施例１のシリコーン化合物成分をシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－５１５）５．２ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３２．１質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が１７．０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が１５．３質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 10)
The same procedure as in Example 1 was carried out except that the silicone compound component in Example 1 was changed to 5.2 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515), and a silicone compound-containing organic solvent silica sol was prepared. (Dynamic light scattering particle size: 21 nm, SiO 2 concentration: 32.1% by mass). The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 17.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 15.3% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
実施例１のシリコーン化合物成分をシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－５１５）５．２ｇに変更した以外は、実施例１と同様に操作を行い、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３２．１質量％）を得た。ＤＭＡＣ分散シリカゾル１Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が１７．０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が１５．３質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 10)
The same procedure as in Example 1 was carried out except that the silicone compound component in Example 1 was changed to 5.2 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515), and a silicone compound-containing organic solvent silica sol was prepared. (Dynamic light scattering particle size: 21 nm, SiO 2 concentration: 32.1% by mass). The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 17.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 15.3% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
（実施例１１）
参考例２で得られたＤＭＡＣ分散シリカゾル２Ａの１００ｇにシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－５１５）２．１ｇを添加し、実施例１と同様に操作を行うことで、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２２ｎｍ、ＳｉＯ2濃度３０．９質量％）を得た。ＤＭＡＣ分散シリカゾル２Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が６．８質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が６．６質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 11)
By adding 2.1 g of silicone oligomer (trade name KR-515, manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 g of DMAC-dispersed silica sol 2A obtained in Reference Example 2, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 22 nm, SiO 2 concentration: 30.9% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 6.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.6% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
参考例２で得られたＤＭＡＣ分散シリカゾル２Ａの１００ｇにシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－５１５）２．１ｇを添加し、実施例１と同様に操作を行うことで、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２２ｎｍ、ＳｉＯ2濃度３０．９質量％）を得た。ＤＭＡＣ分散シリカゾル２Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が６．８質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が６．６質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 11)
By adding 2.1 g of silicone oligomer (trade name KR-515, manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 g of DMAC-dispersed silica sol 2A obtained in Reference Example 2, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 22 nm, SiO 2 concentration: 30.9% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 6.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.6% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
（実施例１２）
参考例２で得られたＤＭＡＣ分散シリカゾル２Ａの１００ｇにシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－５１５）５．２ｇを添加し、実施例１と同様に操作を行うことで、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３２．３質量％）を得た。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸を得た。ＤＭＡＣ分散シリカゾル２Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が１７．０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が１５．２質量％であった。 (Example 12)
By adding 5.2 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515) to 100 g of DMAC-dispersed silica sol 2A obtained in Reference Example 2, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 21 nm, SiO 2 concentration: 32.3% by mass) was obtained. Next, in the same manner as in Example 1, the mixture was mixed with polyamic acid to obtain a silica-containing polyamic acid. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 17.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 15.2% by mass.
参考例２で得られたＤＭＡＣ分散シリカゾル２Ａの１００ｇにシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－５１５）５．２ｇを添加し、実施例１と同様に操作を行うことで、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度３２．３質量％）を得た。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸を得た。ＤＭＡＣ分散シリカゾル２Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が１７．０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が１５．２質量％であった。 (Example 12)
By adding 5.2 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515) to 100 g of DMAC-dispersed silica sol 2A obtained in Reference Example 2, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 21 nm, SiO 2 concentration: 32.3% by mass) was obtained. Next, in the same manner as in Example 1, the mixture was mixed with polyamic acid to obtain a silica-containing polyamic acid. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 17.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 15.2% by mass.
（実施例１３）
参考例３で得られたＤＭＡＣ分散シリカゾル３Ａの１００ｇにシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＣ－８９Ｓ）１０．８ｇを添加し、実施例１と同様に操作を行うことで、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２０ｎｍ、ＳｉＯ2濃度２４．０質量％）を得た。ＤＭＡＣ分散シリカゾル３Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５２．７質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が４０．６質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 13)
By adding 10.8 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KC-89S) to 100 g of DMAC-dispersed silica sol 3A obtained in Reference Example 3, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 20 nm, SiO 2 concentration 24.0% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 3A was 52.7% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 40.6% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
参考例３で得られたＤＭＡＣ分散シリカゾル３Ａの１００ｇにシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＣ－８９Ｓ）１０．８ｇを添加し、実施例１と同様に操作を行うことで、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２０ｎｍ、ＳｉＯ2濃度２４．０質量％）を得た。ＤＭＡＣ分散シリカゾル３Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が５２．７質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が４０．６質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 13)
By adding 10.8 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KC-89S) to 100 g of DMAC-dispersed silica sol 3A obtained in Reference Example 3, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 20 nm, SiO 2 concentration 24.0% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 3A was 52.7% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 40.6% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
（実施例１４）
参考例４で得られたＤＭＡＣ分散シリカゾル４Ａの１００ｇにシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－５１５）１．４ｇを添加し、実施例１と同様に操作を行うことで、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度２１．１質量％）を得た。ＤＭＡＣ分散シリカゾル４Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が６．８質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が６．５質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 14)
By adding 1.4 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515) to 100 g of DMAC-dispersed silica sol 4A obtained in Reference Example 4, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 21 nm, SiO 2 concentration: 21.1% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 4A was 6.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
参考例４で得られたＤＭＡＣ分散シリカゾル４Ａの１００ｇにシリコーンオリゴマー（信越化学工業（株）製、商品名ＫＲ－５１５）１．４ｇを添加し、実施例１と同様に操作を行うことで、シリコーン化合物含有有機溶媒シリカゾル（動的光散乱法粒子径２１ｎｍ、ＳｉＯ2濃度２１．１質量％）を得た。ＤＭＡＣ分散シリカゾル４Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が６．８質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が６．５質量％であった。次いで、実施例１と同様にポリアミック酸と混合することでシリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。 (Example 14)
By adding 1.4 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515) to 100 g of DMAC-dispersed silica sol 4A obtained in Reference Example 4, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 21 nm, SiO 2 concentration: 21.1% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 4A was 6.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
（比較例１）
参考例２で得られたＤＭＡＣ分散シリカゾル２Ａにシリコーン化合物成分を添加せず、実施例１と同様の操作を行うことで、シリカ配合ポリアミック酸を得た。ＤＭＡＣ分散シリカゾル２Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。 (Comparative example 1)
A silica-containing polyamic acid was obtained by performing the same operation as in Example 1 without adding the silicone compound component to the DMAC-dispersed silica sol 2A obtained in Reference Example 2. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
参考例２で得られたＤＭＡＣ分散シリカゾル２Ａにシリコーン化合物成分を添加せず、実施例１と同様の操作を行うことで、シリカ配合ポリアミック酸を得た。ＤＭＡＣ分散シリカゾル２Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。 (Comparative example 1)
A silica-containing polyamic acid was obtained by performing the same operation as in Example 1 without adding the silicone compound component to the DMAC-dispersed silica sol 2A obtained in Reference Example 2. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
（比較例２）
参考例３で得られたＤＭＡＣ分散シリカゾル３Ａにシリコーン化合物成分を添加せず、実施例１と同様の操作を行うことで、シリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。ＤＭＡＣ分散シリカゾル３Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。 (Comparative example 2)
A silica-blended polyamic acid (insulating resin composition) was obtained by performing the same operation as in Example 1 without adding a silicone compound component to DMAC-dispersed silica sol 3A obtained in Reference Example 3. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 3A was 0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
参考例３で得られたＤＭＡＣ分散シリカゾル３Ａにシリコーン化合物成分を添加せず、実施例１と同様の操作を行うことで、シリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。ＤＭＡＣ分散シリカゾル３Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。 (Comparative example 2)
A silica-blended polyamic acid (insulating resin composition) was obtained by performing the same operation as in Example 1 without adding a silicone compound component to DMAC-dispersed silica sol 3A obtained in Reference Example 3. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 3A was 0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
（比較例３）
参考例４で得られたＤＭＡＣ分散シリカゾル４Ａにシリコーン化合物成分を添加せず、実施例１と同様の操作を行うことで、シリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。ＤＭＡＣ分散シリカゾル４Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。 (Comparative example 3)
A silica-blended polyamic acid (insulating resin composition) was obtained by performing the same operation as in Example 1 without adding the silicone compound component to DMAC-dispersed silica sol 4A obtained in Reference Example 4. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 4A was 0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
参考例４で得られたＤＭＡＣ分散シリカゾル４Ａにシリコーン化合物成分を添加せず、実施例１と同様の操作を行うことで、シリカ配合ポリアミック酸（絶縁性樹脂組成物）を得た。ＤＭＡＣ分散シリカゾル４Ａ中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の割合が０質量％であった。 (Comparative example 3)
A silica-blended polyamic acid (insulating resin composition) was obtained by performing the same operation as in Example 1 without adding the silicone compound component to DMAC-dispersed silica sol 4A obtained in Reference Example 4. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 4A was 0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
（比較例４）
実施例１において、シリカゾルとシラン化合物とシリコーン化合物を添加せずに行いポリアミック酸（絶縁性樹脂組成物）を得た。
上記表１～表４において、（シリコーン）は実施例に用いたシリコーン化合物の種類であり一般式で示される式（１）、式（２）、式（３）から選択されるシリコーン化合物に相当するものであった。
(Comparative example 4)
In Example 1, polyamic acid (insulating resin composition) was obtained without adding silica sol, silane compound, and silicone compound.
In Tables 1 to 4 above, (silicone) is the type of silicone compound used in the examples and corresponds to a silicone compound selected from formula (1), formula (2), and formula (3) shown in the general formula. It was something to do.
実施例１において、シリカゾルとシラン化合物とシリコーン化合物を添加せずに行いポリアミック酸（絶縁性樹脂組成物）を得た。
In Example 1, polyamic acid (insulating resin composition) was obtained without adding silica sol, silane compound, and silicone compound.
（シリコーン含有量Ａ）は（式（１）又は式（２）のシリコーン化合物添加前の）有機溶媒シリカゾル中のＳｉＯ２に対する上記シリコーン化合物の含有割合を示し、単位は質量％を記載した。
（シリコーン含有量Ｂ）は（式（１）又は式（２）のシリコーン化合物添加後の）シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対するシリコーン化合物の割合を示し、単位は質量％を記載した。 (Silicone content A) indicates the content ratio of the silicone compound to SiO 2 in the organic solvent silica sol (before addition of the silicone compound of formula (1) or formula (2)), and the unit is mass %.
(Silicone content B) indicates the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol (after addition of the silicone compound of formula (1) or formula (2)), and the unit is mass %.
（シリコーン含有量Ｂ）は（式（１）又は式（２）のシリコーン化合物添加後の）シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対するシリコーン化合物の割合を示し、単位は質量％を記載した。 (Silicone content A) indicates the content ratio of the silicone compound to SiO 2 in the organic solvent silica sol (before addition of the silicone compound of formula (1) or formula (2)), and the unit is mass %.
(Silicone content B) indicates the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol (after addition of the silicone compound of formula (1) or formula (2)), and the unit is mass %.
（シラン官能基）はシリカ粒子に被覆する一般式で示される式（５）乃至式（７）から選択されるシラン化合物の有機官能基の種類を示した。そして（なし）とは上記シラン化合物を添加していない場合を示した。
（樹脂含有量）は窒素含有ポリマー（参考例５で合成したポリアミック酸）の１質量部に対し、上記有機溶媒シリカゾルに含まれるシリカ粒子の割合を示し、単位は質量部であった。そしてゼロである場合は有機溶媒シリカゾルを添加していない場合を記載した。 (Silane functional group) indicates the type of organic functional group of the silane compound selected from formulas (5) to (7) represented by the general formula to be coated on the silica particles. And (none) indicates the case where the above-mentioned silane compound was not added.
(Resin content) indicates the ratio of silica particles contained in the organic solvent silica sol to 1 part by mass of the nitrogen-containing polymer (polyamic acid synthesized in Reference Example 5), and the unit is parts by mass. When it is zero, the case where no organic solvent silica sol is added is described.
（樹脂含有量）は窒素含有ポリマー（参考例５で合成したポリアミック酸）の１質量部に対し、上記有機溶媒シリカゾルに含まれるシリカ粒子の割合を示し、単位は質量部であった。そしてゼロである場合は有機溶媒シリカゾルを添加していない場合を記載した。 (Silane functional group) indicates the type of organic functional group of the silane compound selected from formulas (5) to (7) represented by the general formula to be coated on the silica particles. And (none) indicates the case where the above-mentioned silane compound was not added.
(Resin content) indicates the ratio of silica particles contained in the organic solvent silica sol to 1 part by mass of the nitrogen-containing polymer (polyamic acid synthesized in Reference Example 5), and the unit is parts by mass. When it is zero, the case where no organic solvent silica sol is added is described.
実施例１～１４で得られたシリカ配合ポリアミック酸（絶縁性樹脂組成物）は、比較例１～４に比べて、シリカ配合ポリイミドを焼き付けた硬化膜（絶縁性被膜）の絶縁寿命を向上させることができた。
エナメル線の作製と評価
参考例５で得られたポリアミック酸１３ｋｇを２０Ｌポリ容器に入れ、メカニカルスターラーで攪拌しながら、実施例２に記載したシリコーン化合物含有有機溶媒シリカゾルと同じ方法によって得られたシリコーン化合物含有有機溶媒シリカゾルを１．８ｋｇ、ＤＭＡＣを４．４ｋｇ添加し、室温で１時間攪拌することで、シリカ配合ポリアミック酸（絶縁樹脂組成物、樹脂／ＳｉＯ２＝８０／２０、固形分１５質量％）を得た。 The silica-containing polyamic acids (insulating resin compositions) obtained in Examples 1 to 14 improve the insulation life of cured films (insulating coatings) in which silica-containing polyimide is baked, compared to Comparative Examples 1 to 4. I was able to do that.
Preparation and evaluation of enameled wire 13 kg of the polyamic acid obtained in Reference Example 5 was placed in a 20 L plastic container, and while stirring with a mechanical stirrer, the silicone obtained by the same method as the silicone compound-containing organic solvent silica sol described in Example 2. By adding 1.8 kg of compound-containing organic solvent silica sol and 4.4 kg of DMAC and stirring at room temperature for 1 hour, silica-containing polyamic acid (insulating resin composition, resin/SiO 2 = 80/20, solid content 15 mass) was obtained. %) was obtained.
エナメル線の作製と評価
参考例５で得られたポリアミック酸１３ｋｇを２０Ｌポリ容器に入れ、メカニカルスターラーで攪拌しながら、実施例２に記載したシリコーン化合物含有有機溶媒シリカゾルと同じ方法によって得られたシリコーン化合物含有有機溶媒シリカゾルを１．８ｋｇ、ＤＭＡＣを４．４ｋｇ添加し、室温で１時間攪拌することで、シリカ配合ポリアミック酸（絶縁樹脂組成物、樹脂／ＳｉＯ２＝８０／２０、固形分１５質量％）を得た。 The silica-containing polyamic acids (insulating resin compositions) obtained in Examples 1 to 14 improve the insulation life of cured films (insulating coatings) in which silica-containing polyimide is baked, compared to Comparative Examples 1 to 4. I was able to do that.
Preparation and evaluation of enameled wire 13 kg of the polyamic acid obtained in Reference Example 5 was placed in a 20 L plastic container, and while stirring with a mechanical stirrer, the silicone obtained by the same method as the silicone compound-containing organic solvent silica sol described in Example 2. By adding 1.8 kg of compound-containing organic solvent silica sol and 4.4 kg of DMAC and stirring at room temperature for 1 hour, silica-containing polyamic acid (insulating resin composition, resin/SiO 2 = 80/20, solid content 15 mass) was obtained. %) was obtained.
銅導体（１．０ｍｍ径）に上記のシリカ配合ポリアミック酸を塗布・焼き付けを行い、最終的に厚さ３４μｍの絶縁層を持つ絶縁電線を作製した。
また、参考例６として、銅導体（１．０ｍｍ径）に参考例５で得られたポリアミック酸の塗布・焼き付けを行い、厚さ３６μｍの絶縁層を持つ絶縁電線を作製した。
上記で得られた絶縁電線の可撓性、絶縁寿命（Ｖ－ｔ試験）の評価を実施した。評価方法、条件を下記に示す。 The above silica-containing polyamic acid was applied and baked onto a copper conductor (1.0 mm diameter), and an insulated wire having an insulating layer with a thickness of 34 μm was finally produced.
Further, as Reference Example 6, the polyamic acid obtained in Reference Example 5 was coated and baked on a copper conductor (1.0 mm diameter) to produce an insulated wire having an insulating layer with a thickness of 36 μm.
The flexibility and insulation life (Vt test) of the insulated wire obtained above were evaluated. The evaluation method and conditions are shown below.
また、参考例６として、銅導体（１．０ｍｍ径）に参考例５で得られたポリアミック酸の塗布・焼き付けを行い、厚さ３６μｍの絶縁層を持つ絶縁電線を作製した。
上記で得られた絶縁電線の可撓性、絶縁寿命（Ｖ－ｔ試験）の評価を実施した。評価方法、条件を下記に示す。 The above silica-containing polyamic acid was applied and baked onto a copper conductor (1.0 mm diameter), and an insulated wire having an insulating layer with a thickness of 34 μm was finally produced.
Further, as Reference Example 6, the polyamic acid obtained in Reference Example 5 was coated and baked on a copper conductor (1.0 mm diameter) to produce an insulated wire having an insulating layer with a thickness of 36 μm.
The flexibility and insulation life (Vt test) of the insulated wire obtained above were evaluated. The evaluation method and conditions are shown below.
（可撓性）
ＪＩＳ Ｃ ３２１６－３ ５項に準拠し、皮膜に亀裂が発生しない合格巻き付け倍径を調査した（無伸長及び２０％伸長後のエナメル線で実施）。
可撓性試験（無伸長）は、伸長していない絶縁電線を絶縁電線の導体径の１～１０倍の直径を有する巻き付け棒へ巻き付け、光学顕微鏡を用いて絶縁皮膜に亀裂の発生が見られない最小巻き付け倍径を測定した。
可撓性試験（２０％伸長）は、絶縁電線を２０％伸長した。その後上記（無伸長）と同様の試験を行った。
可撓性試験結果は、亀裂を発生しない最小巻き付け倍径が自己径（１ｄ）、亀裂を発生しない最小巻き付け倍径が自己径の２倍（２ｄ）、亀裂を発生しない最小巻き付け倍径が自己径の３倍（３ｄ）となり、最小巻き付け倍径ｄが小さいほど可撓性に優れているといえる。 (flexibility)
In accordance with JIS C 3216-3 Section 5, the acceptable winding diameter without cracking of the film was investigated (conducted with unstretched and 20% elongated enamelled wires).
In the flexibility test (non-stretching), an unstretched insulated wire is wound around a winding rod with a diameter of 1 to 10 times the conductor diameter of the insulated wire, and cracks are observed in the insulation film using an optical microscope. The minimum winding diameter was measured.
In the flexibility test (20% elongation), the insulated wire was elongated by 20%. Thereafter, the same test as above (no elongation) was conducted.
The flexibility test results show that the minimum winding diameter without cracking is the self-diameter (1d), the minimum winding diameter without cracking is twice the self-diameter (2d), and the minimum winding diameter without cracking is the self-diameter (2d). It is three times the diameter (3d), and it can be said that the smaller the minimum wrapping diameter d is, the better the flexibility is.
ＪＩＳ Ｃ ３２１６－３ ５項に準拠し、皮膜に亀裂が発生しない合格巻き付け倍径を調査した（無伸長及び２０％伸長後のエナメル線で実施）。
可撓性試験（無伸長）は、伸長していない絶縁電線を絶縁電線の導体径の１～１０倍の直径を有する巻き付け棒へ巻き付け、光学顕微鏡を用いて絶縁皮膜に亀裂の発生が見られない最小巻き付け倍径を測定した。
可撓性試験（２０％伸長）は、絶縁電線を２０％伸長した。その後上記（無伸長）と同様の試験を行った。
可撓性試験結果は、亀裂を発生しない最小巻き付け倍径が自己径（１ｄ）、亀裂を発生しない最小巻き付け倍径が自己径の２倍（２ｄ）、亀裂を発生しない最小巻き付け倍径が自己径の３倍（３ｄ）となり、最小巻き付け倍径ｄが小さいほど可撓性に優れているといえる。 (flexibility)
In accordance with JIS C 3216-3 Section 5, the acceptable winding diameter without cracking of the film was investigated (conducted with unstretched and 20% elongated enamelled wires).
In the flexibility test (non-stretching), an unstretched insulated wire is wound around a winding rod with a diameter of 1 to 10 times the conductor diameter of the insulated wire, and cracks are observed in the insulation film using an optical microscope. The minimum winding diameter was measured.
In the flexibility test (20% elongation), the insulated wire was elongated by 20%. Thereafter, the same test as above (no elongation) was conducted.
The flexibility test results show that the minimum winding diameter without cracking is the self-diameter (1d), the minimum winding diameter without cracking is twice the self-diameter (2d), and the minimum winding diameter without cracking is the self-diameter (2d). It is three times the diameter (3d), and it can be said that the smaller the minimum wrapping diameter d is, the better the flexibility is.
（Ｖ－ｔ試験）
ＪＩＳ Ｃ ３２１６－５ ４項に準拠し、２個より試験片を作製し、温度２４０℃の環境下に置いて、２線間に下記電圧を印加し、破壊するまでの時間を計測した。
・電圧：１．５ｋＶ
・周波数：１０ｋＨｚ矩形波
・パルス幅：５μｓ
・両極性
・パルスの立上り時間：８０ｎｓ
参考例６は、ポリアミック酸絶縁樹脂ワニスのみの組成である。
実施例２で得られた絶縁電線は、シリカ無配合のポリアミック酸で被覆した電線に比べて、機械特性を維持しつつ、絶縁寿命を大幅に増加させることができた。 (Vt test)
In accordance with JIS C 3216-5 Section 4, two test pieces were prepared, placed in an environment at a temperature of 240°C, the following voltage was applied between the two wires, and the time until breakage was measured.
・Voltage: 1.5kV
・Frequency: 10kHz square wave ・Pulse width: 5μs
・Bipolar ・Pulse rise time: 80ns
Reference Example 6 has a composition containing only a polyamic acid insulating resin varnish.
The insulated wire obtained in Example 2 was able to significantly increase the insulation life while maintaining mechanical properties compared to the wire coated with silica-free polyamic acid.
ＪＩＳ Ｃ ３２１６－５ ４項に準拠し、２個より試験片を作製し、温度２４０℃の環境下に置いて、２線間に下記電圧を印加し、破壊するまでの時間を計測した。
・電圧：１．５ｋＶ
・周波数：１０ｋＨｚ矩形波
・パルス幅：５μｓ
・両極性
・パルスの立上り時間：８０ｎｓ
実施例２で得られた絶縁電線は、シリカ無配合のポリアミック酸で被覆した電線に比べて、機械特性を維持しつつ、絶縁寿命を大幅に増加させることができた。 (Vt test)
In accordance with JIS C 3216-5 Section 4, two test pieces were prepared, placed in an environment at a temperature of 240°C, the following voltage was applied between the two wires, and the time until breakage was measured.
・Voltage: 1.5kV
・Frequency: 10kHz square wave ・Pulse width: 5μs
・Bipolar ・Pulse rise time: 80ns
The insulated wire obtained in Example 2 was able to significantly increase the insulation life while maintaining mechanical properties compared to the wire coated with silica-free polyamic acid.
本発明はシリコーン化合物を含む有機溶媒シリカゾルであり、それらを用いた絶縁性樹脂組成物と絶縁被覆導線を提供するものである。
The present invention is an organic solvent silica sol containing a silicone compound, and provides an insulating resin composition and an insulated conductor using the same.
The present invention is an organic solvent silica sol containing a silicone compound, and provides an insulating resin composition and an insulated conductor using the same.
Claims (26)
- ５～１００ｎｍの平均一次粒子径を有するシリカ粒子を含む有機溶媒シリカゾルに、式（１）又は式（２）：
式（２）中、Ｒ５はメチル基又はフェニル基を示し、Ｒ７及びＲ８はそれぞれメチル基又はエチル基を示し、Ｒ６はメチル基、エチル基、又は式（３）：
In formula (2), R 5 represents a methyl group or a phenyl group, R 7 and R 8 each represent a methyl group or an ethyl group, and R 6 represents a methyl group, an ethyl group, or a formula (3):
- 上記式（１）のシリコーン化合物が式（４）：
- 上記式（３）中のＲ１０が示すシリコーン化合物が、式（３－１）、式（３－１）及び式（３－２）又は式（３－１）乃至式（３－３）：
- 上記式（１）のシリコーン化合物のｎ１、又は式（４）のシリコーン化合物の（ｎ１１＋ｎ１２）の繰り返し単位が、４～１５である請求項１又は請求項２に記載のシリコーン化合物含有有機溶媒シリカゾル。 The silicone compound-containing organic solvent silica sol according to claim 1 or 2, wherein n1 of the silicone compound of formula (1) or (n11+n12) of the silicone compound of formula (4) has 4 to 15 repeating units.
- 上記の繰り返し単位ｎ２、（ｎ２＋ｎ３）、ｎ１３、ｎ１４又はｎ１５は、式（２）、又は式（３）、式（３－１）、式（３－２）及び式（３－３）を含む式（２）のシリコーン化合物として２５℃で３～３００ｍｍ２／ｓの動粘度を示す条件に該当する繰り返し単位である請求項１又は請求項３に記載のシリコーン化合物含有有機溶媒シリカゾル。 The above repeating unit n2, (n2+n3), n13, n14 or n15 includes formula (2), or formula (3), formula (3-1), formula (3-2) and formula (3-3). The silicone compound-containing organic solvent silica sol according to claim 1 or 3, which is a repeating unit that meets the conditions for the silicone compound of formula (2) to exhibit a kinematic viscosity of 3 to 300 mm 2 /s at 25°C.
- 上記有機溶媒シリカゾル中のＳｉＯ２に対するシリコーン化合物の含有割合が、１～１００質量％である請求項１乃至請求項５の何れか１項に記載のシリコーン化合物含有有機溶媒シリカゾル。 The organic solvent silica sol containing a silicone compound according to any one of claims 1 to 5, wherein the content ratio of the silicone compound to SiO 2 in the organic solvent silica sol is 1 to 100% by mass.
- 上記シリコーン化合物含有有機溶媒シリカゾル中のＳｉＯ２に対するシリコーン化合物の含有割合が、１～１００質量％である請求項１乃至請求項５の何れか１項に記載のシリコーン化合物含有有機溶媒シリカゾル。 The organic solvent silica sol containing a silicone compound according to any one of claims 1 to 5, wherein the content ratio of the silicone compound to SiO 2 in the organic solvent silica sol containing a silicone compound is 1 to 100% by mass.
- 更に式（５）乃至式（７）：
式（６）及び式（７）中、Ｒ２３及びＲ２５はそれぞれ炭素原子数１～３のアルキル基、又は炭素原子数６～３０のアリール基で且つＳｉ－Ｃ結合によりケイ素原子と結合しているものであり、Ｒ２４及びＲ２６はそれぞれアルコキシ基、アシルオキシ基、又はハロゲン基を示し、Ｙはアルキレン基、ＮＨ基、又は酸素原子を示し、ｂは１～３の整数であり、ｃは０又は１の整数であり、ｄは１～３の整数である。）で示される化合物からなる群より選ばれる少なくとも１種のシラン化合物を含むものである請求項１乃至請求項７の何れか1項に記載のシリコーン化合物含有有機溶媒シリカゾル。 Furthermore, formulas (5) to (7):
In formula (6) and formula (7), R 23 and R 25 are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms, and are bonded to a silicon atom through a Si-C bond. R 24 and R 26 each represent an alkoxy group, an acyloxy group, or a halogen group, Y represents an alkylene group, an NH group, or an oxygen atom, b is an integer from 1 to 3, and c is an integer of 0 or 1, and d is an integer of 1 to 3. The silicone compound-containing organic solvent silica sol according to any one of claims 1 to 7, which contains at least one silane compound selected from the group consisting of compounds represented by the following. - 上記式（５）乃至式（７）のシラン化合物中のケイ素原子の個数が、シリカ粒子表面に０．３個／ｎｍ２～５．０個／ｎｍ２の被覆量である請求項１乃至請求項８の何れか１項に記載のシリコーン化合物含有有機溶媒シリカゾル。 Claims 1 to 3, wherein the number of silicon atoms in the silane compounds of formulas (5) to (7) is coated on the surface of the silica particles from 0.3 atoms/nm 2 to 5.0 atoms/nm 2 . The silicone compound-containing organic solvent silica sol according to any one of Item 8.
- 上記シリコーン化合物又はシラン化合物が、シリカ粒子との共有結合を含む請求項１乃至請求項９の何れか1項に記載のシリコーン化合物含有有機溶媒シリカゾル。 The silicone compound-containing organic solvent silica sol according to any one of claims 1 to 9, wherein the silicone compound or silane compound contains a covalent bond with silica particles.
- 上記シリカ粒子が、Ａｌ２Ｏ３に換算して０．００１～２．０質量％／ＳｉＯ２の割合でアルミニウム原子と結合した請求項１乃至請求項１０の何れか１項に記載のシリコーン化合物含有有機溶媒シリカゾル。 The silicone compound according to any one of claims 1 to 10, wherein the silica particles are bonded to aluminum atoms at a ratio of 0.001 to 2.0% by mass/ SiO 2 in terms of Al 2 O 3 Contains organic solvent silica sol.
- 上記シリコーン化合物含有有機溶媒シリカゾルの分散媒が、窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒である請求項１乃至請求項１１の何れか１項に記載のシリコーン化合物含有有機溶媒シリカゾル。 The organic solvent silica sol containing a silicone compound according to any one of claims 1 to 11, wherein the dispersion medium of the organic solvent silica sol containing a silicone compound is a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent. .
- 上記窒素含有溶媒がジメチルアセトアミド、ジメチルホルムアミド、Ｎ－メチルピロリドン、又はＮ－エチルピロリドンであり、カルボニル基含有酸素含有溶媒がγ－ブチロラクトン、又はシクロヘキサノンであり、イオウ含有溶媒がジメチルスルホキシド、又はジメチルスルホンである請求項１乃至請求項１２のいずれか１項に記載のシリコーン化合物含有有機溶媒シリカゾル。 The nitrogen-containing solvent is dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or N-ethylpyrrolidone, the carbonyl group-containing oxygen-containing solvent is γ-butyrolactone or cyclohexanone, and the sulfur-containing solvent is dimethylsulfoxide or dimethylsulfone. The silicone compound-containing organic solvent silica sol according to any one of claims 1 to 12.
- 上記シリコーン化合物含有有機溶媒シリカゾル中のシリカ粒子の動的光散乱法による平均粒子径が５～１００ｎｍである請求項１乃至請求項１３の何れか１項に記載のシリコーン化合物含有有機溶媒シリカゾル。 The silicone compound-containing organic solvent silica sol according to any one of claims 1 to 13, wherein the silica particles in the silicone compound-containing organic solvent silica sol have an average particle diameter of 5 to 100 nm as measured by a dynamic light scattering method.
- 請求項１乃至請求項１４の何れか１項に記載のシリコーン化合物含有有機溶媒シリカゾルと窒素含有ポリマーとを含む組成物。 A composition comprising the silicone compound-containing organic solvent silica sol according to any one of claims 1 to 14 and a nitrogen-containing polymer.
- 請求項１乃至請求項１４の何れか１項に記載のシリコーン化合物含有有機溶媒シリカゾルと窒素含有ポリマーとを含む絶縁性樹脂である組成物。 A composition that is an insulating resin comprising the silicone compound-containing organic solvent silica sol according to any one of claims 1 to 14 and a nitrogen-containing polymer.
- 上記窒素含有ポリマーの１質量部に対し、上記シリコーン化合物含有有機溶媒シリカゾルに含まれるシリカ粒子の配合量が、０．０１～１質量部である請求項１５又は請求項１６に記載の組成物。 The composition according to claim 15 or 16, wherein the amount of silica particles contained in the silicone compound-containing organic solvent silica sol is 0.01 to 1 part by mass with respect to 1 part by mass of the nitrogen-containing polymer.
- 上記窒素含有ポリマーが、ポリイミド、ポリアミド、ポリアミック酸、ポリアミドイミド、ポリエーテルイミド、ポリエステルイミド、又はこれらの混合物である請求項１５乃至請求項１７のいずれか１項に記載の組成物。 The composition according to any one of claims 15 to 17, wherein the nitrogen-containing polymer is polyimide, polyamide, polyamic acid, polyamideimide, polyetherimide, polyesterimide, or a mixture thereof.
- シリカ配合量が７～３０質量％である請求項１５乃至請求項１８の何れか１項に記載の組成物を、０．５ｍｍ厚の銅板上に塗布して層厚３０～３５μｍの絶縁層を形成し、銅板側に密着した円盤電極（直径２５ｍｍ径）と絶縁層側に密着した球状電極（直径２０ｍｍ径）との間に電圧（交流）３．０ｋＶ（周波数５０Ｈｚ）を温度１５５℃とする条件で印加して測定したときの絶縁寿命が８５分以上である組成物。 The composition according to any one of claims 15 to 18, wherein the silica content is 7 to 30% by mass, is coated on a 0.5 mm thick copper plate to form an insulating layer with a layer thickness of 30 to 35 μm. A voltage (AC) of 3.0 kV (frequency 50 Hz) is applied at a temperature of 155° C. between a disk electrode (25 mm diameter) closely attached to the copper plate side and a spherical electrode (20 mm diameter) closely attached to the insulating layer side. A composition having an insulation life of 85 minutes or more when measured under applied conditions.
- 請求項１５乃至請求項１９の何れか1項に記載の組成物により導線を絶縁被覆した絶縁被覆導線。 An insulated conductor wire obtained by insulating and coating the conductor wire with the composition according to any one of claims 15 to 19.
- 下記（Ａ）～（Ｃ）工程：
（Ａ）工程：５～１００ｎｍの平均一次粒子径を有するシリカ粒子を含む炭素原子数１～５のアルコール溶媒シリカゾルを準備する工程、
（Ｂ）工程：（Ａ）工程で得られたシリカゾルに式（５）乃至式（７）の何れか１項に記載のシラン化合物を添加し、添加後２０～１００℃で０．１～４８時間、維持する工程、
（Ｃ）工程：（Ｂ）工程で得られたシリカゾルのアルコール溶媒を窒素含有溶媒、カルボニル基含有酸素含有溶媒、又はイオウ含有溶媒に溶媒置換する工程、
を含む請求項１乃至請求項１４に記載のシリコーン化合物含有有機溶媒シリカゾルの製造方法。 The following steps (A) to (C):
(A) Step: preparing an alcohol solvent silica sol having 1 to 5 carbon atoms containing silica particles having an average primary particle diameter of 5 to 100 nm;
(B) Step: A silane compound according to any one of formulas (5) to (7) is added to the silica sol obtained in step (A), and after the addition, at 20 to 100°C, the silane compound is time, the process of maintaining
(C) step: a step of replacing the alcohol solvent of the silica sol obtained in step (B) with a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent;
A method for producing a silicone compound-containing organic solvent silica sol according to any one of claims 1 to 14. - （Ｂ）工程開始～（Ｃ）工程終了後までの所望の段階において第２級又は第３級アミンを添加する工程（Ｄ）を含む請求項２１に記載のシリコーン化合物含有有機溶媒シリカゾルの製造方法。 The method for producing a silicone compound-containing organic solvent silica sol according to claim 21, comprising the step (D) of adding a secondary or tertiary amine at a desired stage from the start of the step (B) to the end of the step (C). .
- ５～１００ｎｍの平均一次粒子径を有するシリカ粒子を含む炭素原子数１～５のアルコール溶媒シリカゾル〔有機溶媒シリカゾル（ｉ）〕と、上記窒素含有ポリマー〔窒素含有ポリマー（ｉｉ）〕と、請求項１又は請求項２に記載のシリコーン化合物〔シリコーン化合物（ｉｉｉ）〕とを混合する工程（Ｅ）を含む請求項１５乃至請求項１９の何れか１項に記載の組成物の製造方法。 An alcohol solvent silica sol having 1 to 5 carbon atoms [organic solvent silica sol (i)] containing silica particles having an average primary particle diameter of 5 to 100 nm, the above nitrogen-containing polymer [nitrogen-containing polymer (ii)], and the claims 20. The method for producing a composition according to any one of claims 15 to 19, comprising a step (E) of mixing the silicone compound [silicone compound (iii)] according to claim 1 or claim 2.
- 工程（Ｅ）の添加の順が、
上記有機溶媒シリカゾル（ｉ）にシリコーン化合物（ｉｉｉ）を添加し、更に窒素含有ポリマー（ｉｉ）を添加する工程（Ｅ－１）、
有機溶媒シリカゾル（ｉ）に窒素含有ポリマー（ｉｉ）を添加し、更にシリコーン化合物（ｉｉｉ）を添加する工程（Ｅ－２）、又は
窒素含有ポリマー（ｉｉ）にシリコーン化合物（ｉｉｉ）を添加し、更に有機溶媒シリカゾル（ｉ）を添加する工程（Ｅ－３）である請求項２３に記載の組成物の製造方法。 The order of addition in step (E) is
a step (E-1) of adding a silicone compound (iii) to the organic solvent silica sol (i) and further adding a nitrogen-containing polymer (ii);
Step (E-2) of adding the nitrogen-containing polymer (ii) to the organic solvent silica sol (i) and further adding the silicone compound (iii), or adding the silicone compound (iii) to the nitrogen-containing polymer (ii), The method for producing a composition according to claim 23, which is a step (E-3) of further adding an organic solvent silica sol (i). - （Ｅ）工程開始～（Ｅ）工程終了後までの所望の段階において有機溶媒を除去する（Ｆ）工程を含む請求項２４に記載の組成物の製造方法。 The method for producing a composition according to claim 24, comprising the step (F) of removing the organic solvent at a desired stage from the start of step (E) to the end of step (E).
- 上記有機溶媒シリカゾル（ｉ）が式（５）乃至式（７）からなる群より選ばれる少なくとも１種のシラン化合物を含むものである請求項２３乃至請求項２５の何れか１項に記載の組成物の製造方法。
The composition according to any one of claims 23 to 25, wherein the organic solvent silica sol (i) contains at least one silane compound selected from the group consisting of formulas (5) to (7). Production method.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004269668A (en) * | 2003-03-07 | 2004-09-30 | Mitsubishi Rayon Co Ltd | Silica-based composition, resin molding and method for producing the same |
| JP2009059651A (en) * | 2007-09-03 | 2009-03-19 | Osaka City | Silsesquioxane based insulating material |
| JP2018119073A (en) * | 2017-01-26 | 2018-08-02 | 石原ケミカル株式会社 | Hydrophilic coating composition |
| WO2019050008A1 (en) * | 2017-09-07 | 2019-03-14 | 日産化学株式会社 | Silica-containing insulating composition |
| WO2022097694A1 (en) * | 2020-11-04 | 2022-05-12 | 日産化学株式会社 | Aluminum-containing silica sol dispersed in nitrogen-containing solvent, and resin composition |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004269668A (en) * | 2003-03-07 | 2004-09-30 | Mitsubishi Rayon Co Ltd | Silica-based composition, resin molding and method for producing the same |
| JP2009059651A (en) * | 2007-09-03 | 2009-03-19 | Osaka City | Silsesquioxane based insulating material |
| JP2018119073A (en) * | 2017-01-26 | 2018-08-02 | 石原ケミカル株式会社 | Hydrophilic coating composition |
| WO2019050008A1 (en) * | 2017-09-07 | 2019-03-14 | 日産化学株式会社 | Silica-containing insulating composition |
| WO2022097694A1 (en) * | 2020-11-04 | 2022-05-12 | 日産化学株式会社 | Aluminum-containing silica sol dispersed in nitrogen-containing solvent, and resin composition |
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