CN101627043A - Silane compound, production method thereof, and resin composition containing silane compound - Google Patents
Silane compound, production method thereof, and resin composition containing silane compound Download PDFInfo
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- CN101627043A CN101627043A CN200880004127A CN200880004127A CN101627043A CN 101627043 A CN101627043 A CN 101627043A CN 200880004127 A CN200880004127 A CN 200880004127A CN 200880004127 A CN200880004127 A CN 200880004127A CN 101627043 A CN101627043 A CN 101627043A
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- silane compound
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- -1 Silane compound Chemical class 0.000 title claims abstract description 623
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 425
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 84
- 239000011342 resin composition Substances 0.000 title abstract description 43
- 229920005989 resin Polymers 0.000 claims description 298
- 239000011347 resin Substances 0.000 claims description 298
- 150000001875 compounds Chemical class 0.000 claims description 172
- 125000003118 aryl group Chemical group 0.000 claims description 101
- 239000000463 material Substances 0.000 claims description 98
- 150000003949 imides Chemical class 0.000 claims description 85
- 125000000217 alkyl group Chemical group 0.000 claims description 50
- 239000004065 semiconductor Substances 0.000 claims description 46
- 125000000962 organic group Chemical group 0.000 claims description 45
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 43
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 40
- 125000005843 halogen group Chemical group 0.000 claims description 35
- 125000001931 aliphatic group Chemical group 0.000 claims description 28
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 27
- 125000002723 alicyclic group Chemical group 0.000 claims description 23
- 238000006068 polycondensation reaction Methods 0.000 claims description 23
- 125000000623 heterocyclic group Chemical group 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 125000002252 acyl group Chemical group 0.000 claims description 19
- 239000003989 dielectric material Substances 0.000 claims description 12
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 9
- 229910018557 Si O Inorganic materials 0.000 claims description 8
- 229910008051 Si-OH Inorganic materials 0.000 claims description 8
- 229910006358 Si—OH Inorganic materials 0.000 claims description 8
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 abstract description 128
- 229910052710 silicon Inorganic materials 0.000 abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 description 158
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 113
- 239000000126 substance Substances 0.000 description 100
- 239000000543 intermediate Substances 0.000 description 80
- 239000002994 raw material Substances 0.000 description 65
- 229920001187 thermosetting polymer Polymers 0.000 description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 58
- 230000015572 biosynthetic process Effects 0.000 description 56
- 239000003795 chemical substances by application Substances 0.000 description 55
- 238000009833 condensation Methods 0.000 description 47
- 230000005494 condensation Effects 0.000 description 46
- 238000000034 method Methods 0.000 description 46
- 238000003786 synthesis reaction Methods 0.000 description 45
- 238000005160 1H NMR spectroscopy Methods 0.000 description 44
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 43
- 239000004593 Epoxy Substances 0.000 description 43
- 239000007795 chemical reaction product Substances 0.000 description 41
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 40
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 40
- 229910052757 nitrogen Inorganic materials 0.000 description 40
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 38
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 38
- 239000000047 product Substances 0.000 description 37
- 239000006227 byproduct Substances 0.000 description 36
- 238000001035 drying Methods 0.000 description 36
- 239000004840 adhesive resin Substances 0.000 description 33
- 229920006223 adhesive resin Polymers 0.000 description 33
- 229910052761 rare earth metal Inorganic materials 0.000 description 32
- 238000006460 hydrolysis reaction Methods 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 28
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 28
- 239000000843 powder Substances 0.000 description 28
- 230000007062 hydrolysis Effects 0.000 description 27
- 239000006247 magnetic powder Substances 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 24
- 239000000178 monomer Substances 0.000 description 23
- 150000002910 rare earth metals Chemical class 0.000 description 23
- 239000003063 flame retardant Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 20
- 229910045601 alloy Inorganic materials 0.000 description 19
- 239000000956 alloy Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 19
- 230000005291 magnetic effect Effects 0.000 description 19
- 238000000465 moulding Methods 0.000 description 19
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 19
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 18
- 238000006482 condensation reaction Methods 0.000 description 18
- 239000000470 constituent Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 230000006866 deterioration Effects 0.000 description 17
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000002808 molecular sieve Substances 0.000 description 17
- 238000010992 reflux Methods 0.000 description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 16
- 150000008064 anhydrides Chemical class 0.000 description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 150000001721 carbon Chemical group 0.000 description 14
- 230000003301 hydrolyzing effect Effects 0.000 description 14
- 229920001296 polysiloxane Polymers 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 125000003710 aryl alkyl group Chemical group 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 235000019439 ethyl acetate Nutrition 0.000 description 13
- 229920003192 poly(bis maleimide) Polymers 0.000 description 13
- 235000013824 polyphenols Nutrition 0.000 description 13
- 125000005372 silanol group Chemical group 0.000 description 13
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 description 12
- 125000005574 norbornylene group Chemical group 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 239000003566 sealing material Substances 0.000 description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 11
- 239000004305 biphenyl Substances 0.000 description 11
- 230000006837 decompression Effects 0.000 description 11
- 125000003700 epoxy group Chemical group 0.000 description 11
- 239000003822 epoxy resin Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 150000002576 ketones Chemical class 0.000 description 11
- 238000005070 sampling Methods 0.000 description 11
- 239000002966 varnish Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000004567 concrete Substances 0.000 description 10
- 238000009434 installation Methods 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229930185605 Bisphenol Natural products 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- 235000010290 biphenyl Nutrition 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- 239000005011 phenolic resin Substances 0.000 description 9
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 229920000265 Polyparaphenylene Polymers 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 150000001896 cresols Chemical class 0.000 description 8
- 229940079593 drug Drugs 0.000 description 8
- 239000003814 drug Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000005728 strengthening Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 239000011810 insulating material Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000012764 mineral filler Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
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- 239000004033 plastic Substances 0.000 description 7
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229940126062 Compound A Drugs 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000004902 Softening Agent Substances 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 125000005370 alkoxysilyl group Chemical group 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
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- 229910052731 fluorine Inorganic materials 0.000 description 6
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000008442 polyphenolic compounds Chemical class 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 150000004756 silanes Chemical class 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229960000834 vinyl ether Drugs 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 5
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 5
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- PMPBFICDXLLSRM-UHFFFAOYSA-N 1-propan-2-ylnaphthalene Chemical compound C1=CC=C2C(C(C)C)=CC=CC2=C1 PMPBFICDXLLSRM-UHFFFAOYSA-N 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 4
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 229940052303 ethers for general anesthesia Drugs 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
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- 230000001404 mediated effect Effects 0.000 description 4
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 4
- 150000001282 organosilanes Chemical class 0.000 description 4
- 150000003016 phosphoric acids Chemical class 0.000 description 4
- 238000006884 silylation reaction Methods 0.000 description 4
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- 239000007790 solid phase Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 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
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 150000003527 tetrahydropyrans Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- IECKAVQTURBPON-UHFFFAOYSA-N trimethoxymethylbenzene Chemical compound COC(OC)(OC)C1=CC=CC=C1 IECKAVQTURBPON-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The present invention provides a silane compound having a siloxane bond and an imido bond, its production method, and a resin composition containing a silane compound. The silane compound of the present invention comprises a structure unit formed by connecting at least one organic skeleton having an imido bond to a silicon atom forming a siloxane bond and is defined by the particular average composition formula.
Description
Technical field
The resin combination that the present invention relates to silane compound, its production method and comprise silane compound.More specifically, the present invention relates to: the silane compound that can be used for installing purposes, optical applications, optical device purposes, display equipment purposes, mechanical part material, Electrical and Electronic component materials and bonded permanent magnet usefulness thermosetting adhesive resin combination etc.; The silane compound that can be used for their intermediate; The production method of described silane compound; With the resin combination that comprises described silane compound.
Background technology
Silane compound with siloxane bond is the compound with at least one Si-O key (siloxane bond), comprises polysiloxane (being commonly referred to silicone) and polysilsesquioxane, and has been widely used as the raw material of various Industrial products so far.Now, because the characteristic that siloxane bond brings, silane compound has been used to various uses.For example, they have been used to various materials, usefulness, optical device usefulness, display equipment usefulness, mechanical part, Electrical and Electronic parts and trolley part material etc. for example are installed, and optical material, for example optical fiber, optical waveguides, optical recording, blooming and base plate for displaying etc.In described application,, studied the silane compound that can show the characteristic that siloxane bond brings at present always in repeated attempt and error, and in order to be applied to such use in order to transform and improve the various characteristics of the resin that will use.
Summary of the invention
The problem to be solved in the present invention
Silane compound for routine, developed following substances: be characterised in that it has the novel cpd of dimaleoyl imino and alkoxysilyl (for example referring to TOHKEMY 2002-69084 communique page 2 via amino-formate bond, claim 1), silane compound (for example referring to the 9th page in Japanese kokai publication sho 63-146891 communique) with imide, triethoxysilylpropyltetrasulfide-1 as organic absorbing compounds, the 8-naphthalimide is (for example referring to Japanese Unexamined Patent Application Publication 2003-502449 communique page 2, claim 9), poly-Na Dike oxyalkylene imide precursor (polynadic imidesiloxane precursors) (for example referring to Japanese kokai publication hei 09-279034 communique page 5, the 24th section), the bar-shaped polysiloxane (for example referring to TOHKEMY 2006-45392 communique page 2) and the poly-aminoalkyl group silicone composite (for example referring to the 2nd~4 page in TOHKEMY 2005-120333 communique) of stratiform that have ammonium cation on the surface.Yet, still have the space of improvement so that obtain various function excellences and for the compound that can show enough functions such as thermotolerance installing that purposes extremely needs the preferred practicality in the further field of exploitation.
For such as various materials such as mechanical part material, Electrical and Electronic component materials and trolley part materials, except requiring product higher functional (functionality), also require they be can be durable in the material of the application of severe condition.For example, the wide bandgap semiconductor as novel semiconductor material is arranged, as silicon carbide (SiC) and gan (GaN).Compare with the semiconductor device of silicon (Si) type of routine techniques, these semiconductor materials have higher operation ceiling temperature, higher resistance to pressure, in the time of machinery and chemical stability and high thermal conductivity, also be easy to add (doping) impurity and have similitude in many Si manufacturing method for semiconductor device, therefore have realized that, for these semiconductor materials, the technology barrier of manufacturing installation product is lower, and the substrate that these semiconductor materials is used for power semiconductor device makes it possible to achieve higher resistance to pressure, lower power consumption and higher operating temperature and the power loss of semiconductor device reduced half.Thereby these semiconductor materials are used for rectifier cell, household electrical appliances and PC and have obtained promoting with the application of switched power IC, electric vehicle engine driven IC and invertor (inverter) IC.
Especially these years in, power truck and hybrid vehicle become the forward position, with trend development, carried out significant vehicle electricization, strongly need various electronic control units, performer, transmitter and the IC that communicates by letter is integrated, thus and place them in the internal space of maintenance spaciousness in the hot environment of closing on engine and wheel box and leave wider choice to the vehicle interior layout.In addition, with regard to driver who uses with regard to vehicle and user's the security, more stricter than application in domestic appliances to the requirement that prevents mal-operation.Thereby, as the plastic material that is used for mechanical part, electrical and electronic parts and trolley part, required to be and to compare the less plastic material of various physical properties deteriorations in higher temperature range in the past.
Usually, generally in these fields use the epoxies material,, can find these materials weightlessness and physical strength deterioration significantly, thereby need improve thermotolerance if be placed on for a long time up under the temperature more than 200 ℃ for example.Though engineering plastics such as polyimide as high heat-stable material are arranged, the operability of described plastics is relatively poor and be difficult to have as the good processibility of epoxy material, thereby their application is limited to flexible base, board etc.Therefore, these material requires suppress weight loss, have improvement thermotolerance, realize excellent processibility and can be used for various uses.
In addition, though various polysiloxane/polysilsesquioxanes or nano composite material can be used as the example of hybrid inorganic-organic materials, yet these materials improved heat resistance on the whole are not enough or with high costs, because even they have excellent thermotolerance, they also need to contain noble metal catalyst in use, thereby these materials are not suitable for as a large amount of consumer applications (for example referring to the 2nd~4 page in TOHKEMY 2006-73950 communique) such as automobiles.
Bonded permanent magnet typically refers to the magnet that generates by with following resin combination moulding, described resin combination comprise as magnetic materials such as ferrite, alnico and rare earth and as described in the tackiness agent of matrix of magnetic substance.Compare with the conventional magnet that generates by sintering process usually, described bonded permanent magnet is easy to moulding, and can be shaped to complicated shape with high precision.Thereby the purposes of described bonded permanent magnet extends to rapidly in the various application.For example, bonded permanent magnet has been used to various products and assembly, for example automobile, ordinary appliances, signal equipment, and audio-frequency apparatus, medical equipment and general industry equipment.
Usually make the mixture solidified and the moulding of magnetic substance and adhesive resin by thermoforming step (as injection molding and extrusion moulding), thereby make bonded permanent magnet.In this case, in injection molding for example, described mixture is exposed to 200 ℃~300 ℃ high temperature.In addition, if be used for the electric vehicle engine, then the agglutinating magnet need move under the high temperature more than 200 ℃ recently.In this case, have following technical problem: magnet surface is oxidized and be coated with oxide compound, and described thermal history has reduced the Coercive Force of magnetic substance.
For the resin combination that is used for magnet agglutinating routine, for example, TOHKEMY 2001-206926 communique page 1 and page 2 have proposed can solidify at low temperatures in moulding process and need not be exposed to the pyritous resin combination.This resin combination is the rare earth composite that is used for bonded permanent magnet, and it comprises (A) makes in the epoxy compounds 50%~100% epoxy group(ing) carry out vinyl ester with unsaturated monoprotic acid and adhesive resin that the polymerizable compound that obtains is formed, (B) thermal polymerization and (C) rare earth alloy powder.In addition, for example, TOHKEMY 2003-217915 communique page 2 discloses the high-weatherability magnet powder, described powder comprises the phosphoric acid salt coating (B2) that phosphoric acid salt coating (B1) that average film thickness is 5nm~10nm and average film thickness are 5nm~100nm on the surface of magnet powder (A), described magnet powder (A) is made up of the ferro-magnetic powdered alloy that contains rare earth element, the iron of wherein said phosphoric acid salt coating (B1)/rare earth element ratio is more than or equal to 5 and less than 8, and the iron of described phosphoric acid salt coating (B2)/rare earth element ratio is more than or equal to 8.In addition, Japanese Unexamined Patent Application Publication 2003-217916 communique page 2 discloses the high heat resistance magnet powder, and wherein average film thickness is that the copper coating (B1) of 1nm~10nm and inorganic phosphate coating (B2) that average film thickness is 5nm~10nm are formed on the surface of the magnet powder of being made up of the transition metal magnet powdered alloy that comprises rare earth element (A) successively.Attempted on the magnet powder surface, forming the phosphorus coating, thereby in moulding process, suppressed the oxidation on bonded permanent magnet surface, and then avoided the deterioration of magnetic properties.Yet, thereby described performance need further improve fully solve conventional bonded permanent magnet as problems such as thermotolerances.Thereby described conventional bonded permanent magnet has and improves the field that the space strongly needing to be preferred for exploitation, and the application of using bonded permanent magnet at present.
Under above-mentioned prior art, the resin combination that the present invention is devoted to provide the silane compound and the production method thereof of thermotolerance, resistance to pressure, machinery and chemical stability and excellent thermal conductivity and contains silane compound, described compound can be advantageously be used to install purposes with the form of following resin combination, even even described resin combination is used bigger shearing force or in as harsh and unforgiving environments such as high temperature and high pressures, described resin combination also can form the various physical propertiess solidify material of deterioration not substantially.
The means of dealing with problems
The inventor has carried out various researchs to silane compound, and found to have the silane compound of the organic backbone that comprises imide key and amido bond, described silane compound is incorporated into described organic backbone by Siliciumatom via Sauerstoffatom and forms siloxane backbone.The inventor has been found that the resin combination that comprises described compound and organic resin can demonstrate excellent thermotolerance and the excellent specific property that do not lose this organic resin and had, light as product weight, make product ability, formability and flexibility closely, thereby realize above-mentioned target.In addition, the inventor has been found that the resin combination that comprises described silane compound and organic resin can be particularly advantageous for the installation purposes of various materials, and described material for example has mechanical component materials, Electrical and Electronic component materials, trolley part material and bonded permanent magnet compositions of thermosetting resin.In addition, the High-efficient Production that also has that the inventor has been found that has the method for the silane compound of described concrete structure, and has finally finished the present invention.
In other words, the invention provides silane compound with siloxane bond and imide key, thereby wherein said silane compound comprises by making at least one organic backbone with imide key be connected the structural unit that forms with the Siliciumatom that forms siloxane bond, and wherein said silane compound is limited by a following average group accepted way of doing sth:
XaYbZcSiOd
In this formula,
X can be identical or different, and expression is by the group that comprises the organic backbone with imide key of following formula (1) representative; Z can be identical or different, and expression does not have the organic group of imide key; Y can be identical or different, and expression is selected from least a group in the group of being made up of hydrogen atom, hydroxyl, halogen atom and OR group; R can be identical or different, and expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and can have substituting group; A is less than or equal to 3 but be not 0 number; B is 0 or less than 3 number; C is 0 or less than 3 number; D is less than 2 number but is not 0; And a+b+c+2d=4,
In this formula, R
1Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring; X and z can be identical or different, represent 0~5 integer independently; And y is 0 or 1.
Below, the present invention will be described particularly.
Thereby silane compound of the present invention has by making at least one organic backbone with imide key be connected structural unit (hereinafter, being also referred to as structural unit (I)) and the siloxane bond (siloxane backbone) that forms with Siliciumatom.Because above-mentioned silane compound (being also referred to as silane compound (i)) has such structure, so described silane compound has excellent thermotolerance, resistance to pressure, machinery and chemical stability and thermal conductivity, and can provide as various characteristicses such as thermotolerances various materials.For example, can suitably select as siloxane backbone, organic backbone and structural unit (I) with imide key thus etc. structure obtain having silane compound with the high-compatibility of various polymkeric substance, thereby be easy to provide thermotolerance and resistance to pressure to described polymkeric substance.The also curing article of deterioration seldom of various physical propertiess can be formed under even be provided the described polymkeric substance of thermotolerance and resistance to pressure, thereby purposes can be preferred for installing as severe rugged environments such as high temperature and high pressures.As mentioned above, above-mentioned silane compound can be preferred for mechanical part material, Electrical and Electronic component materials, trolley part material, civil engineering work and material of construction, formed material and coating and tackiness agent material, also can be as electronic material with formed material and ink, coating, varnish and tackiness agent material.In addition, above-mentioned silane compound can be as used dielectric materials in the semiconductor device etc., or as the bonded permanent magnet compositions of thermosetting resin.Especially, described compound can be preferred for than household electrical appliance with conventional material need have high thermal stability more such as enforcement fields such as state-of-the-art microprocessor unit (MPU) and vehicle installing materials.
In the above-mentioned silane compound (i), " organic backbone with imide key " is not subjected to concrete restriction, as long as this structure must have the imide key, yet it is preferably, and (1) contains the structure of the alkylidene group of imide structure and 1~6 carbon atom, (2) contain the structure of imide structure and secondary amino group and the structure that (3) contain imide structure and uncle's amino.Especially, more preferably (1) contains the structure of the alkylidene group of imide structure and 1~6 carbon atom, and this is because it has provided the silane compound with high thermal stability.
In above-mentioned silane compound (i), with respect to 100 moles of contained in the above-mentioned silane compound (i) Siliciumatoms, above-mentioned ratio with organic backbone of imide key is preferably 20 moles~100 moles.Its more preferably 50 moles~100 moles, and then more preferably 70 moles~100 moles, especially be preferably 80 moles~100 moles, most preferably be 100 moles.In view of the above, can improve solubleness and thermotolerance and the hydrolytic resistance etc. of described silane compound to organic resin.
The Siliciumatom that is connected to above-mentioned organic backbone with imide key except with also be connected organic backbone that at least one has an imide key is connected with at least one Sauerstoffatom, and form siloxane backbone by Sauerstoffatom.Promptly, the Siliciumatom that is connected to the organic backbone with imide key is connected in organic backbone with imide key, Sauerstoffatom and optional other skeleton, with the key of described organic backbone, Sauerstoffatom and other skeleton add up to 4, and organic backbone quantitatively all is connected one at least with Sauerstoffatom.
Other skeleton can comprise and is selected from least a in the group of being made up of the organic group that does not have the imide key, hydrogen atom, hydroxyl, halogen atom and OR group.R can be identical or different, and expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and can have substituting group.The described organic group that does not have imide is preferably at least a group that is selected from the group of being made up of alkyl, aromatic residue (as aryl and aralkyl) and unsaturated aliphatic residue, and these groups can have substituting group.Especially preferred example is to have substituent alkyl, aromatic residue (as aryl or aralkyl) with 1~8 carbon atom in case of necessity.These organic groups can have substituting group.Practical example is methyl, ethyl, phenyl, vinyl, chloropropyl, sulfydryl propyl group, (epoxycyclohexyl) ethyl, glycidoxypropyl, N-phenyl-3-aminopropyl, (methyl) acryloxy propyl group, hexyl, decyl, octadecyl and trifluoro propyl.
The above-mentioned quantity with organic backbone of imide key that is connected with Siliciumatom is 1~3, is preferably 1~2, more preferably 1.The quantity of the Sauerstoffatom that is connected (being connected to the Sauerstoffatom of the Siliciumatom that is connected with the organic backbone with imide key) is 1~3, is preferably 2~3, more preferably 3.The quantity of other organic backbone that is connected is 0~2, is preferably 0~1, more preferably 0.Count (1,3,0), (2,2,0), (1,2,1), (3,1,0), (2,1,1) and (1,1,2) with the preferred combination (bond number) of Siliciumatom bonded skeleton (group) with (organic backbone with imide key, Sauerstoffatom, other skeleton).
Above-mentioned silane compound (i) has siloxane backbone (being also referred to as main chain backbone).This siloxane backbone can comprise any skeleton, as long as these skeletons must have siloxane bond, and the structure of siloxane backbone can be chain or branching, and preferably has the polysilsesquioxane of ladder structure, cage structure or cubic structure.
With respect to the silane compound (i) of 100 weight %, the ratio of siloxane backbone is preferably 10 weight %~80 weight %, more preferably 15 weight %~70 weight % in the above-mentioned silane compound (i), and then more preferably 20 weight %~50 weight %.
Above-mentioned silane compound (i) is not subjected to concrete restriction, as long as this compound has said structure, the example of preferred implementation can be: (1) has the silane compound of siloxane bond and imide key, wherein said silane compound comprise must have siloxane bond (polysiloxane key) main chain backbone and have by making the structure that must contain the imide key be connected the structure that forms with described main chain backbone; (2) must have the silane compound of following structural unit, at least one organic backbone with imide key is connected with Siliciumatom and at least one Sauerstoffatom is connected with above-mentioned Siliciumatom among the described structural unit, and wherein the above-mentioned Siliciumatom of structural unit forms siloxane backbone by Sauerstoffatom; (3) have main chain backbone that comprises siloxane bond and silane compound with organic backbone of imide key, wherein this silicon compound contains following structural unit as requisite unit, and this structural unit is to be connected with described organic backbone by some Siliciumatoms that make described main chain backbone to form; (4) comprise siloxane bond and silane compound with organic backbone of imide key, wherein said silane compound comprises the main chain backbone that must have the polysiloxane key, and described organic backbone with imide key is connected with at least one Siliciumatom of described main chain backbone.
In above-mentioned preferred implementation (1), " being connected the structure that forms with described main chain backbone by making the structure that must contain the imide key " can comprise by making at least one structure that must contain the imide key (organic backbone with imide key) be connected the structure that forms with the main framing (siloxane backbone) of described silane compound (i).That is, this structure can comprise: also have the above-mentioned structure that must contain the structure of imide key except that described main chain backbone.Particularly, preferably those have the silane compound of the structure that must contain the imide key to above-mentioned silane compound (i) in side chain.In this case, the described structure that must contain the imide key is not limited to those structures that contains the repeating unit of formation " chain " shape structure, but also comprises that those have the structure of at least one structure as side chain.
In above-mentioned preferred implementation (2), " wherein at least one has the structural unit that organic backbone is connected with Siliciumatom and at least one Sauerstoffatom is connected with above-mentioned Siliciumatom of imide key " limited by following general formula preferably:
In this formula, X represents to have the organic backbone of imide key; S is 1~3 integer; 2t is 1~3 integer; And s+2t=4.
Above-mentioned silane compound is limited by a following average group accepted way of doing sth preferably:
XaYbZcSiOd
In this formula,
X can be identical or different, and expression has the organic backbone of imide key; Z can be identical or different, and expression does not have the organic backbone of imide key; Y can be identical or different, and expression is selected from least a group in the group of being made up of hydrogen atom, hydroxyl, halogen atom and OR group; R can be identical or different, and expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and can have substituting group; A is less than or equal to 3 but be not 0 number; B is 0 or less than 3 number; C is 0 or less than 3 number; D is less than 2 but is not 0 number; And a+b+c+2d=4.That is, the coefficient a of X is the number that satisfies 0<x≤3; The coefficient b of Y is the number that satisfies 0≤y<3; The coefficient c of Z is the number that satisfies 0≤z<3; And the coefficient d of O is to satisfy the number of 0<d<2.Above-mentioned formula (1) is described below.
In above-mentioned silane compound,, then can improve the solubleness of this silane compound to organic resin if having of the ratio increase of the organic backbone of imide key with respect to Siliciumatom.From the solubleness to organic resin, preferably the coefficient a of X satisfies more than or equal to 0.2 in a described average group accepted way of doing sth.If less than 0.2, then the solubleness to organic resin may reduce as the coefficient a of the X of the organic backbone with imide key.Therefore, if thereby above-mentioned silane compound is dissolved in organic resin forms resin combination, and then this resin combination may not can fully shows the characteristic that described silane compound brings.The coefficient a of X more preferably greater than or equal 0.5, and then more preferably greater than or equal 0.7, especially be preferably greater than or equal 0.8, most preferably more than or equal to 1.0.From the thermotolerance of above-mentioned silane compound, coefficient a preferably is less than or equal to 1.0.If coefficient a is greater than 1.0, then the functional group except that X is connected with Si, thereby may make the thermotolerance deterioration.As mentioned above, preferably the coefficient a of X satisfies 0.2~1.0, thereby makes described resin combination have the solubleness and the excellent hydrolytic resistance to organic resin of more excellent thermotolerance, improvement.The coefficient a of X more preferably 0.5~1.0, and then more preferably 0.7~1.0, and is especially preferred 0.8~1.0, most preferably is 1.0.In an above-mentioned average group accepted way of doing sth, a+b+c is preferably greater than or equals 0.5, more preferably greater than or equal 0.7, and then more preferably 0.7~1.0, especially preferred 1.The coefficient d of oxygen is preferably 1.50.
The ratio of the silanol base unit weight of preferably calculating by following formula (α) in the described silane compound is less than or equal to 0.1.
[mole number of Si-OH key]/[mole number of Si-O key] (α)
In view of the above, the composition that comprises above-mentioned silane compound has significantly low viscosity.In addition, described composition and curing article thereof can obtain extremely excellent anti-water absorbability.The silanol base unit weight that is calculated by following formula (α) preferably is less than or equal to 0.05, and then is more preferably less than or equals 0.01.Especially preferred is that above-mentioned silane compound does not have residual silanol group.Herein, the mole number of Si-OH key is meant the Si that represents with mole number and the quantity of the key between the OH.For example, if with respect to every mole, each Si atom is connected with two OH groups, and then the mole number of Si-OH key is 2.In an identical manner, also can calculate the mole number of Si-O key.
In above-mentioned average group accepted way of doing sth XaYbZcSiOd: Y is preferably hydroxyl or OR group.Y is the OR group more preferably, so more preferably wherein R be OR group with alkyl of 1~8 carbon atom.In addition, Z is preferably a kind of group that is selected from the group of being made up of aromatic residue (as alkyl, aryl and aralkyl) and unsaturated aliphatic residue.They can have substituting group.Z is more preferably has substituent aromatic residue in case of necessity, as has alkyl, the aryl or aralkyl of 1~8 carbon atom.
Above-mentioned silane compound for example can be defined as follows:
In this formula, X, Y and Z can be identical or different independently, and same as above; n
1And n
2The expression polymerization degree, n
1Be positive integer but be not 0 and n
2Be 0 or positive integer.Thus, Y/Z represents to be connected with Y or Z:X
1-2-expression is connected with 1 or 2 X groups: (Z/Y)
1-2-expression is connected with 1 Z or Y group, or is connected with 2 Z or Y group, perhaps is connected with totally 2 groups, and wherein Z and Y group are each one: Si-(X/Y/Z)
3Represent that any three X, Y are connected with Siliciumatom with the Z group.In above-mentioned formula, Si-Om
1And Si-Om
2Do not limit Si-Om
1And Si-Om
2Bond order, but preferably limit for example Si-Om
1And Si-Om
2Reciprocal (reciprocal) or random copolycondensation state and Si-Om
1Polysiloxane and Si-Om
2The bonding state of polysiloxane, and the condensation structure is arbitrarily.
Can be with an above-mentioned average group accepted way of doing sth: X
aY
bZ
cSiO
dLimit above-mentioned silane compound; And the siloxane backbone of described silane compound (backbone structure that must have siloxane bond) can be restricted to (SiO
m)
nRemove (SiO
m)
nStructure in addition comprises: as the organic backbone with imide key (structure that must have the imide key) of X; As the hydrogen atom of Y or hydroxyl etc.; As the organic group that does not have the imide key of Z, and they are connected with Siliciumatom.X, Y and Z can be involved or can be comprised among the repeating unit that forms with " chain ".For example, in individual molecule, can comprise at least one X as side chain.At above-mentioned (SiO
m)
nIn, n represents the polymerization degree, it shows that quantitatively needn't there be n in the main chain backbone and the polymerization degree with organic backbone of imide key.In other words, for each (SiO
m)
n, needn't have organic backbone one by one with imide key.In addition, in a molecule, can there be one or more organic backbones with imide key, in the situation that comprises a plurality of organic backbones with imide key, as mentioned above, a Siliciumatom can be connected with the organic backbone that has the imide key more than two.
At above-mentioned main framing (SiO
m)
nIn, m is preferably more than or equal to 1.0 and less than 2.0 number, more preferably m=1.5~1.8, especially preferred m=1.5.At above-mentioned main chain backbone (SiO
M1)
N1(SiO
M2)
N2In, (n preferably
1+ 1)/(n
1+ n
2+ 1) scope is identical with the preferable range of a among the above average group accepted way of doing sth XaYbZcSiOd.In addition, preferably be connected to (X/Y/Z) in the following formula
3The Si atom and (SiOm
1) in the quantity of the X that is connected of Si atom be 1.
Above-mentioned label symbol n represents the polymerization degree, and is preferably 1~5000.More preferably 1~2000, more preferably 1~1000, and then n=1~200 more preferably.
Be that described silane compound can comprise under 2 the situation at n: comprise two by the structural unit (structural unit (I)) that at least one organic backbone with imide key is connected with Siliciumatom form silane compound and only comprise the silane compound of a structural unit.Practical example is as follows:
In this formula, A represents Y or Z; And X, Y and Z are same as above, can comprise: those have the group, those groups with the homopolymer structure that comprises two different structure unit (I) of the homopolymer structure that comprises two same structure unit (I) and those have the group of the copolymer structure (copolycondensation structure) that only comprises a structural unit (I).
Silane compound of the present invention (silane compound (i)) has said structure, and the X in the average group accepted way of doing sth of above-mentioned silane compound is limited by above-mentioned formula (1).
The silane compound that " X in the average group accepted way of doing sth of above-mentioned silane compound is limited by above-mentioned formula (1) " expression has an average group accepted way of doing sth, the X among a wherein above-mentioned average group accepted way of doing sth: the XaYbZcSiOd (Z, Y, a, b, c and d are as mentioned above) is limited by formula (1).Hereinafter, it is suitable for following formula (2) equally.
At above-mentioned R
1In, at least a structure that is selected from the group of being made up of aromatic nucleus, heterocycle and alicyclic ring is meant R
1Expression is selected from by the group (aromatic nucleus) of the ring structure with aromatic series part, has the group (heterocycle) of the ring structure of heterocyclic moiety and have at least a group in the group that the group (cycloaliphatic ring) of the ring structure of alicyclic moiety forms.R
1Be preferably phenylene, naphthylidene, divalence norbornylene group, (alkyl) cyclohexylidene and cyclohexenyl.At R
1Be under the situation of phenylene, can obtain the silane compound that wherein above-mentioned X is limited by following formula (2); At R
1Be under the situation of (alkyl) cyclohexylidene, can obtain the silane compound that wherein above-mentioned X is limited by following formula (3); At R
1Be under the situation of naphthylidene, can obtain the silane compound that wherein above-mentioned X is limited by following formula (4); At R
1Be under the situation of divalence norbornylene group, can obtain the silane compound that wherein above-mentioned X is limited by following formula (5); At R
1Be under the situation of cyclohexenyl, can obtain the silane compound that wherein above-mentioned X is limited by following formula (6).
In above-mentioned formula (1), x and z can be identical or different, represent 0~5 integer independently.
In addition, x+y can be 0~10 integer, and is preferred 3~7, more preferably 3~5, and then more preferably 3.
Above-mentioned y is 0 or 1 and be preferably 0.
Above-mentioned silane compound (1) can be preferred for the application described in the above-mentioned silane compound (i), and especially be preferred for than the conventional material needs that are used for household electrical appliance more high thermal stability such as enforcement fields such as state-of-the-art MPU and vehicle installing materials.In addition, above-mentioned silane compound (1) have very high thermotolerance and with the high-compatibility of various polymkeric substance, thereby it can easily provide thermotolerance.In fact, in silane compound being added to such as various materials such as aromatic series plastics to improve in the stable on heating situation, needn't adopt the addition means (adding described silane compound in material dispersion therein then) of silicone compounds routine, for example, silane compound can be added in advance in the raw material of various polymkeric substance and make described raw material reaction, make silane compound can be mixed and provide excellent thermotolerance more equably to obtain various polymkeric substance.In this manner, if above-mentioned silane compound (1) is added in the heat-resisting aromatic series plastics, then can further improve thermotolerance, these plastics can be preferred for such use.
Can produce the silane compound (i) that limits by above-mentioned average group accepted way of doing sth XaYbZcSiOd with any method, yet, described silane compound preferably by following production method (a) and (b) obtained.(a) production method comprises intermediate (silane compound) imidization that will be limited by average group accepted way of doing sth X ' aYbZcSiOd, described intermediate comprises organic backbone X ' and the siloxane bond with amido bond, and described have the organic backbone X ' of amido bond corresponding to the organic backbone X with imide key in the above-mentioned silane compound (i); (b) production method comprises intermediate hydrolysis and the condensation that makes following silane compound, among described intermediate, the organic backbone with imide key corresponding with the organic backbone X with imide key in the above-mentioned silane compound (i) is connected with Siliciumatom, and described intermediate has hydrolysable group.
Above-mentioned silane compound (1) preferably obtains by the production method that comprises the intermediate imidization that will be made up of following silane compound, described silane compound by average group accepted way of doing sth X ' aYbZcSiOd (X ' expression has the organic backbone of amido bond; Identical in other symbol and the above-mentioned average group accepted way of doing sth) limit, wherein X ' is limited by following formula (8); Perhaps, above-mentioned silane compound (1) preferably obtains by the production method that comprises the step that makes the intermediate hydrolysis be made up of following silane compound and polycondensation, and described silane compound is limited by following formula (10).These production methods will be described below.
Above-mentioned silane compound is preferably (in silane compound (i) or (1)) and satisfies the silane compound of following requirement (being also referred to as silane compound (2)), and the X in the average group accepted way of doing sth of above-mentioned silane compound is limited by following formula (2):
In this formula, R
2~R
5Can be identical or different, expression is selected from least a group in the group of being made up of hydrogen atom, alkyl, halogen atom or aromatic base independently; X and z can be identical or different, represent 0~5 integer independently; And y is 0 or 1.
Above-mentioned R
2~R
5Preferably be hydrogen atom.
Above-mentioned x, y and z are preferably with above described identical.
Above-mentioned silane compound is preferably (in silane compound (i) or (1)) and satisfies the silane compound of following requirement (being also referred to as silane compound (3)), and the X in the average group accepted way of doing sth of above-mentioned silane compound is limited by following formula (3):
In this formula, R
6~R
9And R
6 '~R
9 'Can be identical or different, expression is selected from least a group in the group of being made up of hydrogen atom, alkyl, halogen atom or aromatic base independently; X and z can be identical or different, represent 0~5 integer independently; And y is 0 or 1.
For above-mentioned R
6~R
9And R
6 '~R
9 ', R preferably
7Or R
8Be that methyl and all the other are hydrogen atom, or R
6~R
9And R
6 '~R
9 'Be hydrogen atom, or R
6~R
9And R
6 '~R
9 'Be fluorine atom.R more preferably
7Or R
8Be that methyl and all the other are hydrogen atom.
Above-mentioned x, y and z are preferably with above described identical.
Above-mentioned silane compound is preferably (in silane compound (i) or (1)) and satisfies the silane compound of following requirement (being also referred to as silane compound (4)), and the X in the average group accepted way of doing sth of above-mentioned silane compound is limited by following formula (4):
In this formula, R
10~R
15Can be identical or different, expression is selected from least a group in the group of being made up of hydrogen atom, alkyl, halogen atom or aromatic base independently; X and z can be identical or different, represent 0~5 integer independently; And y is 0 or 1.
For above-mentioned R
10~R
15, R preferably
10~R
15Be hydrogen atom, or R
10~R
15Be fluorine atom.R more preferably
10~R
15Be hydrogen atom.
Above-mentioned x, y and z are preferably with above described identical.
Above-mentioned silane compound is preferably (in silane compound (i) or (1)) and satisfies the silane compound of following requirement (being also referred to as silane compound (5)), and the X in the average group accepted way of doing sth of above-mentioned silane compound is limited by following formula (5):
In this formula, R
16~R
21Can be identical or different, expression is selected from least a group in the group of being made up of hydrogen atom, alkyl, halogen atom or aromatic base independently; X and z can be identical or different, represent 0~5 integer independently; And y is 0 or 1.
For above-mentioned R
16~R
21, R preferably
16~R
21Be hydrogen atom, or R
16~R
21Be fluorine atom.R more preferably
16~R
21Be hydrogen atom.
Above-mentioned x, y and z are preferably with above described identical.
Above-mentioned silane compound is preferably (in silane compound (i) or (1)) and satisfies the silane compound of following requirement (being also referred to as silane compound (6)), and the X in the average group accepted way of doing sth of above-mentioned silane compound is limited by following formula (6):
In this formula, R
22~R
25And R
22 '~R
25 'Can be identical or different, expression is selected from least a group in the group of being made up of hydrogen atom, alkyl, halogen atom or aromatic base independently; X and z can be identical or different, represent 0~5 integer independently; And y is 0 or 1.
For above-mentioned R
22~R
25And R
22 '~R
25 ', R preferably
22~R
25And R
22 '~R
25 'Be hydrogen atom, or R
22~R
25And R
22 '~R
25 'Be fluorine atom, or R
22~R
25And R
22 '~R
25 'Be the chlorine atom.More preferably be hydrogen atom.
Above-mentioned x, y and z are preferably with above described identical.
Each comfortable intramolecularly of above-mentioned silane compound (5) and (6) comprises unsaturated link(age) and forms crosslinking structure by the mechanism identical with following maleimide compound.Thereby, if every kind is mixed in maleimide compound and silane compound (5) and (6), then this mixture can be used as resin combination, and shows excellent low dielectric characteristics, this mainly is because this crosslinking structure is the saturated rings structure, does not generate polar group after crosslinked.That is, preferably described resin combination is the resin combination that is used for dielectric materials.Compound (5) is preferably as described silane compound.In the normal ratio of unsaturated link(age), the ratio of mixture of described silane compound and above-mentioned maleimide is 10/90~90/10, more preferably 15/85~85/15, and then more preferably 20/80~80/20.
The preference that above-mentioned resin combination is used for the application of dielectric materials comprises the printed circuit board (PCB) that is used for high-speed computing machine or high speed communication equipment, the radio communication antenna that is used for Wi-Fi, WiMAX, bluetooth and RF label etc., the satellite broadcasting converter printed circuit board (PCB) is used for the sheet material and the storage card of semiconductor packages.If the above-mentioned resin combination that will comprise described silane compound and organic resin then for example can suppress to form the stray capacitance that generates between the electrode of electronic installation as the dielectric materials in the described application.As a result, in this electronic installation, can improve response characteristic and inhibition heating.
The preferably above-mentioned resin combination that is used for dielectric materials has in the survey frequency of 1GHz or 5GHz and is less than or equal to 3.4 relative permittivity.Described relative permittivity is more preferably less than or equals 3.2, and then is more preferably less than or equals 3.1.The preferably described resin combination that is used for dielectric materials has in the survey frequency of 1GHz or 5GHz and is less than or equal to 0.02 tangent of the dielectric loss angle.Described tangent of the dielectric loss angle is more preferably less than or equals 0.01, and then is more preferably less than or equals 0.009.Therefore, have less relative permittivity or less tangent of the dielectric loss angle if be used for the resin combination of dielectric materials, then described resin combination can show the excellent characteristic that is used for above-mentioned application.
If above-mentioned resin combination is the resin combination that is used for dielectric materials, then preferably described resin combination comprises silane compound and maleimide compound.In view of the above, can reduce the value of tangent of the dielectric loss angle.Therefore, in the electronic installation of uses such as the sheet material that is used for semiconductor packages, can improve response characteristic or can suppress heating.In addition, above-mentioned resin combination can comprise other compound except silane compound and maleimide compound.For example, can comprise epoxy compounds and phenolic compound etc.If this resin combination comprises at least a in Resins, epoxy and the phenol resins, then the specific inductivity of this resin combination can be reduced, thereby makes described resin combination can show more excellent characteristic as the resin combination that is used for dielectric materials.
In above-mentioned silane compound (silane compound (i) and (1)~(6)),
X in the average group accepted way of doing sth of above-mentioned silane compound is limited by following formula (7):
In this formula, R
26Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring.
Above-mentioned R
26Preferably with the explanation of above-mentioned silane compound (1) in the R that describes
1Identical.
The especially preferred example of above-mentioned silane compound is: R wherein
26Be poly-(γ-Phthalimide base propyl group silsesquioxane) of phenylene, R wherein
26Be poly-{ γ-(six hydrogen-4-dimethylamino methyl phenyl imide) propyl group silsesquioxane } of methyl cyclohexylidene, R wherein
26Be poly-{ γ-(1,8-naphthalimide base) propyl group silsesquioxane } of naphthylidene, R wherein
26Be divalence norbornylene group poly-γ-(5-norbornylene-2,3-imide) propyl group silsesquioxane) and R
26Be cyclohexenyl poly-[(suitable-4-tetrahydrobenzene-1, the 2-imide) propyl group silsesquioxane).Can pass through
1H-NMR,
13C-NMR, MALDI-TOF-MS measure and discern the structure of these compounds.
Preferably being connected with the Siliciumatom of X and the quantity of the key between the Sauerstoffatom is 3.Like this, the Siliciumatom that is connected with X is not connected with other functional group, thereby above-mentioned silane compound has excellent thermotolerance, wet fastness and hydrolytic resistance.For example, be connected in an oxygen and also be connected in another functional group if be connected with the Siliciumatom of X, then thermotolerance, wet fastness and hydrolytic resistance may depend on the kind of described functional group and reduce.Preferably forming the Siliciumatom of siloxane bond and the quantity of the key between the Sauerstoffatom is 3.Thus, the Siliciumatom of formation siloxane chain only is connected in the organic group by the X representative.Thereby described silicone compounds can have more excellent thermotolerance and hydrolytic resistance.
Since the molecular structure of above-mentioned silane compound can example chain-like structure (straight chain or branching), ladder structure, reticulated structure, ring texture are arranged and comprise the ring texture and the cage structure of ladder structure, preferably trapezoidal, netted and cage structure among them is even this is because the addition of above-mentioned silane compound seldom also causes effect easily.Preferred molecular structure is according to desired effect and difference, for example, by forming the water absorbability that the cage type molecular structure can further reduce the viscosity of the composition that comprises silane compound and significantly suppress the curing article of said composition, can further reduce the viscosity of the composition that comprises silane compound and significantly improve the thermotolerance of the curing article of said composition by forming trapezoidal molecular structure, but can not significantly suppress water absorbability.That is, in order to reduce viscosity and to suppress water absorbability, cage type molecular structure preferably, and as described, above-mentioned silane compound with trapezoidal molecular structure also is a preferred implementation of the present invention.Have the cage type molecular structure and can cause comprising the remarkable reduction of viscosity of the composition of above-mentioned silane compound, described composition or its solidify article and become very excellent on agent of low hygroscopicity, the physical strength of these curing article and thermotolerance can further improve simultaneously, therefore said composition can be used for various uses (especially, electronic unit and device, as be used for semi-conductive sealing material).If molecular structure has ladder structure, the composition that then comprises silane compound has lower viscosity.In addition, it solidifies the thermotolerance that article have obtained remarkable improvement, does not obviously observe stable on heating this improvement although compare with hygroscopic reduction.That is to say that preferred implementation of the present invention comprises that wherein above-mentioned silane compound has the embodiment of trapezoidal molecular structure.Herein, above-mentioned trapezoidal, netted and cage type molecular structure is limited by following structural formula:
In this formula, R represents the organic backbone that limited by " XaYbZc " in the above-mentioned average group accepted way of doing sth.
Said structure formula (a) is random (netted) structure (random structure); Structural formula (b) is trapezoidal shape structure (ladder structure); Structural formula (c) is incomplete cage structure (a not exclusively condensation situation); Structural formula (d)~(f) is cage structure (a condensation structure fully).
As above-mentioned structural formula (c)~(f) institute example, the silane compound with above-mentioned cage type molecular structure preferably comprises organic backbone layer that forms the shell part and the inorganic bone rack-layer that forms the nuclear part.
Silane compound with above-mentioned cage type molecular structure is preferably the silane compound that has as the ring structure of X in the above-mentioned average group accepted way of doing sth, especially be preferably the silane compound that X is wherein limited by above-mentioned general formula (1), that is the above-mentioned silane compound (1) that, has trapezoidal molecular structure.Preferred silane compound is to have at least a structure that is selected from the group of being made up of aromatic nucleus, saturated alicyclic hydrocarbon and unsaturated lipid cyclic hydrocarbon as the R in the above-mentioned general formula (1)
1Silane compound.By making silane compound have above-mentioned structure, can fully cause above-mentioned effect: make the composition that contains above-mentioned silane compound have significantly reduced viscosity, it is significantly excellent aspect agent of low hygroscopicity that described composition and its solidify article.The example of described aromatic nucleus has benzene, biphenyl, terphenyl, naphthalene, En He perylene; The example of described saturated alicyclic hydrocarbon has tetramethylene, pentamethylene, hexanaphthene, cyclooctane, norbornane and naphthane; And described unsaturated alicyclic example has cyclobutene, cyclopentenes, tetrahydrobenzene, cyclooctene and norbornylene.
Have X that the above-mentioned silane compound of trapezoidal molecular structure more preferably wherein limits by above-mentioned general formula (1) and represent silane compound by above-mentioned general formula (2)~structure that (7) limit, be above-mentioned silane compound (2)~(7), and especially be preferably the R in the wherein above-mentioned general formula (1)
1The silane compound of expression phenyl ring or norbornylene structure.
The R of wherein above-mentioned general formula (1)
1An example of the silane compound of expression norbornylene structure is limited by following formula.
If described silane compound has the cage type molecular structure, then the ratio of the silanol base unit weight of more preferably calculating by following formula (α) is less than or equal to 0.1.
[mole number of Si-OH key]/[mole number of Si-O key] (α)
In view of the above, the composition that contains above-mentioned silane compound has significantly low viscosity.In addition, described composition or its curing article have extremely excellent anti-water absorbability.Can show this operation and effect more fully.The ratio of silanol base unit weight and then be more preferably less than or equal 0.05 especially preferably is less than or equal to 0.01.
Most preferably, above-mentioned silane compound does not contain residual silanol group.
In the case, in the above-mentioned average group accepted way of doing sth, a+b+c is preferably greater than or equals 0.5, more preferably greater than or equal 0.7, and then be preferably 0.7~1.0, especially be preferably 1.The coefficient d of oxygen is preferably 1.50.
The present invention also provides the silane compound with siloxane bond and amido bond, and wherein said silane compound is limited by a following average group accepted way of doing sth:
X’aYbZcSiOd:
In this formula, X ' can be identical or different, and expression has the organic backbone of amido bond; Z can be identical or different, and expression does not have the organic backbone of amido bond; Y can be identical or different, and expression is selected from least a group in the group of being made up of hydrogen atom, hydroxyl, halogen atom and OR group; R can be identical or different, and expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and can have substituting group; A is less than or equal to 3 number but is not 0; B is 0 or less than 3 number; C is 0 or less than 3 number; D is less than 2 but is not 0 number; And a+b+c+2d=4), and the silane compound that limits by following formula (8) of the X ' in the preferably wherein said average group accepted way of doing sth:
In this formula, R
27Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring; X and z can be identical or different, represent 0~5 integer independently; And y is 0 or 1.As described, the X ' of a wherein above-mentioned average group accepted way of doing sth (X ' aYbZcSiOd) is an embodiment of the invention by the silane compound that above-mentioned formula (8) limits.
Therein in the intermediate (8) that X ' is limited by above-mentioned formula (8), R
27Be preferably phenylene, naphthylidene, norbornylene and cyclohexylidene.Label symbol x, y and z are preferably x=0 or 2, y=0 or 1 and z=3, more preferably x=0, y=0 and z=3.Thus, Y, Z, a, b, c and d preferably with above-mentioned silane compound (1) in identical.In fact, Y is preferably hydroxyl or OR group, OR group more preferably, and then the OR alkyl of 1~8 carbon atom more preferably.Z is preferably at least a group that is selected from the group of being made up of alkyl, aromatic residue (as aryl and aralkyl) and unsaturated aliphatic residue.These groups can have substituting group.Its alkyl that more preferably has 1~8 carbon atom maybe can have substituent aromatic residue (as aryl or aralkyl).
The molecular structure of above-mentioned silane compound with siloxane bond and amido bond is similar to the above-mentioned silane compound with siloxane bond and imide key, and preferred molecular structure is also according to required effect and difference.Preferably and be connected with the Siliciumatom of X ' and the quantity of the key between the Sauerstoffatom is 3.Preferably forming the Siliciumatom of siloxane bond and the quantity of the key between the Sauerstoffatom is 3.Preferably the silanol base unit weight of calculating by following formula (α) in described silane compound is less than or equal to 0.1.
[mole number of Si-OH key]/[mole number of Si-O key] (α)
The silanol base unit weight of being calculated by following formula (α) is more preferably less than or equals 0.05, and then is more preferably less than or equals 0.01.Especially preferred is that above-mentioned silane compound does not contain residual silanol group.Similarly, in order to reduce viscosity and to realize agent of low hygroscopicity, cage type molecular structure preferably, and therefore, above-mentioned silane compound with cage type molecular structure is one of preferred implementation of the present invention.The R among the X ' in the preferably above-mentioned average group accepted way of doing sth in described silane compound with cage type molecular structure
27With the R among the X in the above-mentioned silane compound with siloxane chain and imide key
1Identical.Preferably described silane compound has ring structure.As mentioned above, described silane compound further preferably has at least a structure that is selected from the group of being made up of aromatic nucleus, saturated alicyclic hydrocarbon and unsaturated lipid cyclic hydrocarbon as the R in the above-mentioned general formula (8)
27, and then more preferably have phenyl ring and norbornylene structure as the R in the above-mentioned general formula (8)
27
R wherein
27An example of the compound that is limited by above-mentioned general formula (8) of expression norbornylene structure is limited by following formula.
As mentioned above, above-mentioned silane compound with cage type molecular structure also is preferably the silane compound with remaining silanol group, and in this case, the organic backbone that is defined as " X ' aYbZc " is preferably 1: 1 with the mol ratio of " Si ", and be at the ratio of organic backbone and " Si " under 1 mole the situation, preferably the ratio of " O (Sauerstoffatom) " is 1.5 moles.
The present invention also provides the silane compound with siloxane bond and amido bond, and wherein said silane compound is limited by following formula (9):
In this formula, R
28Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring; R
29Can be identical or different, the expression organic group; R
30Can be identical or different, expression is selected from hydrogen atom, hydroxyl, halogen atom and OR
30 'At least a group in the group; R
30 'Can be identical or different, expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and can have substituting group; X and z can be identical or different, represent 0~5 integer independently; Y is 0 or 1, and p is 0~2 integer.
In the above-mentioned formula (9), R
29Be preferably phenylene, naphthylidene, norbornylene and cyclohexylidene.R
28Be preferably the organic group that does not contain amido bond.In fact, it is preferably at least a group that is selected from the group of being made up of alkyl, aromatic residue (as aryl and aralkyl) and unsaturated aliphatic residue.These groups can have substituting group.The alkyl that more preferably has 1~8 carbon atom maybe can have substituent aromatic residue (as aryl or aralkyl).These organic groups can have substituting group.And then more preferably methyl or ethyl.R
30Be preferably hydroxyl or OR
30 'Group, more preferably OR
30 'Group, further R wherein more preferably
30 'Group is the OR with alkyl of 1~8 carbon atom
30 'Group, and then R wherein more preferably
30 'Be the OR of methyl, ethyl or propyl group
30 'Group.Label symbol x, y and z are preferably x=0 or 2, y=0 or 1 and z=3, and more preferably x=0, y=0 and z=3, p is integer 0 or 1.
The present invention also provides the silane compound with siloxane bond and imide key, and wherein said silane compound is limited by following formula (10):
In this formula, R
31Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring; R
32Can be identical or different, the expression organic group; R
33Can be identical or different, expression is selected from hydrogen atom, hydroxyl, halogen atom and OR
33 'At least a group in the group; R
33 'Can be identical or different, expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and can have substituting group; X and z can be identical or different, represent 0~5 integer independently; Y is 0 or 1, and q is 0~2 integer.
In the above-mentioned formula (10), R
31Be preferably phenylene, naphthylidene, norbornylene and cyclohexylidene.R
32Be preferably the organic group that does not contain the imide key.In fact, it is preferably at least a group that is selected from the group of being made up of alkyl, aromatic residue (as aryl and aralkyl) and unsaturated aliphatic residue.These groups can have substituting group.The alkyl that more preferably has 1~8 carbon atom maybe can have substituent aromatic residue (as aryl or aralkyl).These organic groups can have substituting group.And then more preferably methyl or ethyl.R
33Be preferably hydroxyl or OR
33 'Group, more preferably OR
33 'Group, further R wherein more preferably
33 'Group is the OR with alkyl of 1~8 carbon atom
33 'Group, and then R wherein more preferably
33 'Be the OR of methyl, ethyl or propyl group
33 'Group.Label symbol x, y and z are preferably x=0 or 2, y=0 or 1 and z=3, and more preferably x=0, y=0 and z=3, q is integer 0 or 1.
The production method of above-mentioned intermediate (8)~(10) is not specifically limited, yet, preferably produce these intermediates by following production method.It is having of preferred implementation of the present invention equally: the intermediate of producing by the following production method that comprises production process (II-1) or production process (II-2) (8); The intermediate of producing by the following production method that comprises production process (III-1) (9); With the intermediate of producing by the following production method that comprises production process (V-1) or production process (V-2) (10).
The present invention also provides the silane compound production method that is used to produce above-mentioned silane compound.
In fact preferably above-mentioned silane compound production method comprises following operation (I)~(V).Owing to comprise these operations, have following advantage: the suitability of the suitability of industrial available materials, industrial production operation and effective production of producing route and intermediate by selection.
For aforementioned production method, the invention provides the method that is used to produce above-mentioned silane compound (silane compound (1) that above-mentioned silane compound (i) or above-mentioned formula (1) limit), wherein said production method is the method that is used to produce silane compound (silane compound (1) or silane compound (i)) that comprises following intermediate imidization, and described intermediate is made up of the silane compound that a following average group accepted way of doing sth limits:
X’aYbZcSiOd
In this formula, X ' can be identical or different, and expression has the organic backbone of amido bond; Z can be identical or different, and expression does not have the organic backbone of amido bond; Y can be identical or different, and expression is selected from least a group in the group of being made up of hydrogen atom, hydroxyl, halogen atom and OR group; R can be identical or different, and expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and can have substituting group; A is less than or equal to 3 number but is not 0; B is 0 or less than 3 number; C is 0 or less than 3 number; D is less than 2 but is not 0 number; And a+b+c+2d=4; In this formula, the X ' in the described average group accepted way of doing sth is limited by following formula (8):
In this formula, R
27Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring; X and z can be identical or different, represent 0~5 integer independently; And y is 0 or 1." intermediate that the silane compound that is limited by formula (8) by X ' is wherein formed " is meant X ' wherein is used as intermediate by the silane compound that formula (8) limits.Above-mentioned Y, Z, a, b, c and d be identical with described in the above-mentioned average group accepted way of doing sth respectively preferably, and above-mentioned R
27, x, y and z preferably respectively with the R described in the above-mentioned silane compound (1)
1, x, y be identical with z.
For aforementioned production method (being also referred to as production method (I)), this method is not subjected to concrete restriction, as long as it comprises the imidization operation (being also referred to as imidization operation (I)) of the intermediate (hereinafter being also referred to as intermediate (8)) that is limited by above-mentioned formula (8).Imidization operation (I) is that the dehydration ring closure by amido acid reacts the operation with described intermediate imidization, and reaction conditions is as follows.
The temperature of reaction of above-mentioned imidization operation is preferably 80 ℃~300 ℃.More preferably 100 ℃~200 ℃, and then preferably remain on more than the azeotropic temperature of water and solvent, this is because water generates as by product.Reaction pressure can be for environmental stress, pressurize or vacuumize, yet, because being shifted out reaction system effectively, the water that is generated promotes reaction fully, thereby environmental stress or vacuumize preferably.In fact, the pressure of preferred 0.01MPa~0.5MPa.
As catalysts, can use known and effective amine usually, as pyridine, triethylamine, imidazoles diaza-bicyclo undecylene or tetramethylphosphonihydroxide hydroxide amine etc., and preferred adding is such as toluene and dimethylbenzene etc. and water azeotropic solvent.
Different though the reaction times is formed with reaction with temperature of reaction, but be preferably 2 hours~48 hours.
Aforementioned production method (production method (I)) preferably includes and makes the intermediate hydrolysis that the silane compound that limited by following formula (9) forms and the operation of polycondensation:
In this formula, R
28Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring; R
29Can be identical or different, the expression organic group; R
30Can be identical or different, expression is selected from hydrogen atom, hydroxyl, halogen atom and OR
30 'At least a group in the group; R
30 'Can be identical or different, expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and can have substituting group; X and z can be identical or different, represent 0~5 integer independently; Y is 0 or 1, and p is 0~2 integer.
In other words, described production method (being also referred to as production method (II)) comprises that also the intermediate (being also referred to as intermediate (9)) that is limited by above-mentioned formula (9) obtains the operation (being also referred to as operation (II-1)) of intermediate (8) except comprising imidization operation (I).Thus, R
28, x, y and z preferably respectively with the R described in the above-mentioned silane compound (1)
1, x, y be identical with z.In addition, R
29And R
30Preferably with above-mentioned R
29And R
30Identical.Label symbol p is preferably 0 or 1.
Above-mentioned operation (II-1) be by intermediate (9) thus the hydrolysis of alkoxysilyl and polycondensation form the operation that the polysiloxane skeleton obtains intermediate (8).
If comprise above-mentioned operation (II-1), then owing to formed the intermediate with high-hydrophilic (9) as the precursor of intermediate (8) (intermediate that limits by following formula (9)), so the hydrolysis of alkoxysilyl and the reaction efficiency of polycondensation are improved, thus the extent of polymerization of increase polysiloxane skeleton.
In the above-mentioned operation (II-1), intermediate (9) can be mixed hydrolysis and the condensation of carrying out intermediate (9) with water or aqueous organic solvent.
Can form polysiloxane skeleton by described hydrolysis and condensation as the product of hydrolysis and condensation.The product of described hydrolysis and condensation is the compound that the condensation reaction of the product that obtained by hydrolysis reaction by further promotion obtains.
Below, shown the hydrolysis reaction and the condensation reaction of intermediate (9).
SiR
29 p(OR
30 ')
3-p+ (3-p) H
2O (hydrolysis) → SiR
29 p(OH)
3-p+ (3-p) R
30 'OH
SiR
29 p(OH)
3-p→ SiR
29 p(OH)
eO
u→ SiR
29 pO
2/u(condensation product)
In this formula, R
29, R
30With p such as above-mentioned, and e and u can be any number.
Can make intermediate (9) hydrolysis and condensation by the way, thereby obtain the higher intermediate with polysiloxane skeleton (8) of the polymerization degree.
In said hydrolyzed and condensation reaction, used water, and this reaction is preferably undertaken by the water with respect to intermediate (9) adding 10 weight %~50 weight % of 100 weight %.The water that more preferably adds 20 weight %~40 weight %.
The water that is used for above-mentioned reaction can be any water, the water of adjusting as ion exchanged water or through pH etc., however preferably using pH is about 7 water.Use such water can reduce the amount of the ionic impurity in the composition and obtain having the resin combination of agent of low hygroscopicity and high-insulativity.With regard to the purity of water, pH 7 is better, yet can be with pH regulator in 2~12 scope, and this is because at high temperature hydrochloric acid, oxalic acid, pyridine or triethylamine are evaporated out outside the reaction system.
The use of above-mentioned water can be by dropwise adding entry or the disposable water that adds carries out in intermediate (9).
The said hydrolyzed of alkoxysilyl and the temperature of reaction of polycondensation are preferably room temperature to 200 ℃, room temperature to 100 ℃ more preferably, and then more preferably remain on the azeotropic reflux temperature of alcohol, water and solvent, this is owing to alcohol generates as by product.Reaction pressure can be normal pressure or pressurization or decompression, yet, can promote reaction fully because the alcohol that is generated is discharged reaction system effectively, thereby preferably be less than or equal to normal pressure.In addition, different though the reaction times is formed with reaction with temperature of reaction, however be preferably 2 hours~48 hours.
The intermediate (hereinafter being also referred to as intermediate (12)) that can limit by following formula (12) by the X in the above-mentioned average group accepted way of doing sth is wherein produced above-mentioned intermediate (8):
In this formula, x and z can be identical or different, represent 0~5 integer independently; And y is 0 or 1.The operation (being also referred to as operation (II-2)) that is obtained intermediate (8) by above-mentioned intermediate (12) also is one of preferred implementation.At intermediate (12) is in the situation of poly-(gamma-amino propyl group) silsesquioxane, and intermediate (12) has higher water-soluble, and the organic solvent that does not have abundant solubleness at present.In operation (II-2), intermediate (12) and anhydride reaction, however when having water, described reaction is owing to the hydration ring-opening reaction of acid anhydrides is suppressed, thereby the productive rate of intermediate (8) is not high enough to carry out industrial with low cost production.Thereby, be in the situation of poly-(gamma-amino propyl group) silsesquioxane at intermediate (12), suitable is to utilize the operation (I) of producing above-mentioned silane compound (1) via operation (II-1).
Above-mentioned label symbol x, y are preferably identical with x, y and the z described in the above-mentioned silane compound (1) respectively with z.
Above-mentioned operation (II-2) is the operation that is obtained intermediate (8) by intermediate (12), and preferably the operation with the introducing amido acid structure of following operation (III-1) is identical usually for this reaction conditions.
The production method of above-mentioned intermediate (9) is not subjected to concrete restriction, yet preferably the compound that is limited by following formula (13) (being called compound (13)) obtains intermediate (9).Promptly, the open loop addition that aforementioned production method (production method (II)) preferably includes the compound that following formula (13) is limited by acid anhydrides obtains the operation (being also referred to as operation (III-1)) of the intermediate is made up of the silane compound that formula (9) limits, perhaps the operation (being also referred to as operation (III-2)) by the intermediate that compound hydrolysis that following formula (13) limits and polycondensation obtained be made up of the silane compound of formula (12) qualification X wherein:
In this formula, R
36Can be identical or different, the expression organic group; R
37Can be identical or different, expression is selected from hydrogen atom, hydroxyl, halogen atom and OR
37 'At least a group in the group; R
37 'Can be identical or different, expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and can have substituting group; X and z can be identical or different, represent 0~5 integer independently; Y is 0 or 1, and v is 0~2 integer.
In other words, described production method (being also referred to as production method (III)) is except comprising the imidization operation, comprise that also hydrolysis and polycondensation step (II-1) or amido acid structure introduce operation (II-2), and obtain the operation (operation (III-1)) of intermediate (9) or obtain the operation (operation (III-2)) of intermediate (12) by compound (13) by compound (13).Comprise that the advantage that described operation causes is to utilize cheap raw material to produce.Label symbol x, y are preferably identical with the z indication with symbol x, the y described in the above-mentioned silane compound (I) independently with z.In addition, R
36, R
37With v preferably independently with the R described in the above-mentioned silane compound (9)
29, R
30Identical with the p indication.
Above-mentioned operation (III-1) is the open loop addition operation that is obtained intermediate (9) by compound (13), and reaction conditions is as follows.
About the water concentration in the above-mentioned operation (III-1), preferably with solvent and reaction unit drying, and circulation-supplied exsiccant nitrogen during reaction, this is because the productive rate of target compound can reduce owing to the hydration of acid anhydrides.Before the reaction can by use dewatering agent (as molecular sieve, anhydrous magnesium sulfate and Calcium Chloride Powder Anhydrous) known and commonly used or by distill dry as described in solvent.
The temperature of reaction of above-mentioned operation is preferably room temperature to 100 ℃, more preferably 40 ℃~90 ℃.This reaction even also fully obtain promoting in room temperature, yet, depending on reaction product, product can during reaction be separated out, and this is in the situation that can cause undermixing in some cases, thereby preferably reacts under than the high slightly temperature of room temperature.The pressure of above-mentioned operation can or vacuumize for environmental stress or pressurization.Different though the reaction times is formed with reaction with temperature of reaction, but be preferably about 2 hours~48 hours.
Above-mentioned operation (III-2) be by compound (13) thus the hydrolysis of alkoxysilyl and polycondensation form the operation that the polysiloxane skeleton obtains intermediate (12), reaction conditions is preferably identical with above-mentioned operation (II-1).
The preferred implementation of aforementioned production method (III) can be method (embodiment (A)) that comprises operation (III-1), operation (II-1) and operation (I) and the method (embodiment (B)) that comprises operation (III-2), operation (II-2) and operation (I).Especially, in embodiment (B), under the situation of gathering (gamma-amino propyl group) silsesquioxane that forms as intermediate (12), more preferably adopt embodiment (A).
Above-mentioned embodiment (A) be comprise by acid anhydrides opening by compound (13) obtain intermediate (9) (operation (III-1)), by making intermediate (9) hydrolysis and polycondensation obtain intermediate (8) (operation (II-1)) and by making intermediate (8) imidization obtain the method for silane compound (i) or silane compound (1).In addition, above-mentioned embodiment (B) is to comprise by making compound (13) hydrolysis and polycondensation obtain intermediate (12) (operation (III-2)), obtain intermediate (8) (operation (II-2)) and by making intermediate (8) imidization obtain the method for silane compound (i) or silane compound (1) by intermediate (12).
Preferred implementation of the present invention also is the method for the following above-mentioned silane compound of production (above-mentioned silane compound (i) or the silane compound (1) that is limited by above-mentioned formula (1)), wherein said production method is the method that comprises the production silane compound that makes following intermediate hydrolysis and condensation, and wherein said intermediate is made up of the silane compound that following formula (10) limits:
In this formula, R
31Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring; R
32Can be identical or different, the expression organic group; R
33Can be identical or different, expression is selected from hydrogen atom, hydroxyl, halogen atom and OR
33 'At least a group in the group; R
33 'Can be identical or different, expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and can have substituting group; X and z can be identical or different, represent 0~5 integer independently; Y is 0 or 1, and q is 0~2 integer.Above-mentioned R
31, x, y and z preferably independently with the R described in the above-mentioned silane compound (1)
1, x, y be identical with the z indication.In addition, R
32, R
33With q preferably independently with the R described in the above-mentioned silane compound (9)
29, R
30Identical with the p indication.
The production method (being also referred to as production method (IV)) that comprises above-mentioned operation is not subjected to concrete restriction, makes intermediate (hereinafter being called intermediate (the 10)) hydrolysis that limited by above-mentioned formula (10) and the operation (being also referred to as hydrolysis and polycondensation step (IV)) of polycondensation as long as it comprises.Hydrolysis is identical with above-mentioned operation (II-1) with reaction conditions in the polycondensation step (IV).Comprising that hydrolysis and polycondensation step (IV) make can use highly purified in advance intermediate (10), thereby the operation that the favourable part of this method is to remove the impurity of the silane compound (1) that is obtained is omitted.
Aforementioned production method (production method (IV)) preferably includes the operation that the compound that is limited by following formula (11) obtains the intermediate be made up of the silane compound that above-mentioned formula (10) limits:
In this formula, A represents halogen atom or isocyanate group; R
34Can be identical or different, the expression organic group; R
35Can be identical or different, expression is selected from hydrogen atom, hydroxyl, halogen atom and OR
35 'At least a group in the group; R
35 'Can be identical or different, expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and can have substituting group; X and z can be identical or different, represent 0~5 integer independently; Y is 0 or 1, and r is 0~2 integer.
In other words, described production method (being also referred to as production method (V)) also comprises the operation (being also referred to as operation (V)) that is obtained intermediate (10) by compound (11) except comprising hydrolysis and polycondensation step (IV).The favourable part that comprises described operation is that the raw material that many kinds are used to introduce the imide skeleton can select.Label symbol x, y are preferably identical with the z indication with x, the y described in the above-mentioned silane compound (1) independently with z.In addition, R
34, R
35With r preferably independently with the R described in the above-mentioned silane compound (9)
29, R
30Identical with the p indication.
In operation (V), be that operation (V-1) is the imidization operation of isocyanate group, preferably following reaction conditions in the situation of isocyanate group (being also referred to as operation (V-1)) at the A of compound (11).
About the water concentration in the above-mentioned operation (V-1), preferably solvent and reaction unit are carried out drying, and circulation-supplied exsiccant nitrogen during reaction, this is because the productive rate of target compound can reduce owing to the hydrolysis of isocyanate group.Before the reaction can by use dewatering agent (as molecular sieve, anhydrous magnesium sulfate and Calcium Chloride Powder Anhydrous) known and commonly used or by distill dry as described in solvent.The temperature of reaction of above-mentioned operation is preferably 60 ℃~250 ℃, more preferably 120 ℃~180 ℃.Depend on reaction product, product can during reaction be separated out, thereby makes and can't stir reaction system, thereby a little higher than room temperature of temperature of reaction.The pressure of above-mentioned operation can be normal pressure or pressurization or decompression.Owing to generated the carbonic acid gas with the amount of branch subnumber such as raw material, so reaction unit is preferably open system as by product.Different though the reaction times is formed with reaction with temperature of reaction, but preferably be about 2 hours~48 hours.
In above-mentioned operation (V), be that operation (V-2) is the imidization operation of haloalkyl, preferably following reaction conditions in the situation of halogen atom (being also referred to as operation (V-2)) at the A of compound (11).
The temperature of reaction of above-mentioned operation (V-2) is preferably room temperature to 150 ℃, more preferably 40 ℃~120 ℃.Depend on reaction product, reaction product can during reaction be separated out, thereby makes and can't stir reaction system, thereby preferably carries out described reaction in the temperature higher than room temperature.
Preferably in above-mentioned operation (V-2), add as catalysts can with the salifiable basic cpd of hydrogen halide shape, for example, carbonate is as salt of wormwood, cesium carbonate, Quilonum Retard and yellow soda ash; Deacidite; And aminated compounds, as triethylamine, pyridine, diaza-bicyclo undecylene.Addition is preferably more than the five equilibrium subnumber of raw material.After the reaction, owing to salt is separated out in reaction soln, preferably by filtering, washing the desalination of making a return journey with water washing or with alcohol.Exist in reaction raw materials in the situation of alkoxysilyl, the preferred employing filtered operation.
The pressure of above-mentioned operation can be normal pressure or pressurization or decompression.Owing to generated as carbonic acid gas by product and amount branch subnumber such as raw material, so reaction unit is preferably open system.Different though the reaction times is formed with reaction with temperature of reaction, but the reaction times be adjustablely also preferably be about 2 hours~48 hours.
The preferred implementation of aforementioned production method (V) can be the method (embodiment (C)) that comprises operation (V-1) and operation (IV) and comprise operation (V-2) and the method for operation (IV) (embodiment (D)).
Above-mentioned embodiment (C) is to comprise by A wherein it being that the compound (11) of isocyanate group obtains intermediate (10) (operation (V-1)) and makes intermediate (10) thereby the method for hydrolysis and polycondensation acquisition silane compound (i) or silane compound (1).In addition, above-mentioned embodiment (D) be comprise by A wherein be the compound (11) of halogen atom obtain intermediate (10) (operation (V-2)) and by making intermediate (10) thus hydrolysis and polycondensation obtain the method for silane compound (i) or silane compound (1).
For the method that obtains silane compound of the present invention (1), above-mentioned embodiment (A)~(D) is preferred, especially with regard to industrial safety and low cost production and high yield, and more preferably embodiment (A), (C) and (D).And then embodiment (A) more preferably.
In aforementioned production method (I)~(V), described method comprises: the operation (operation (II-1), (III-2) and (IV)) that forms siloxane backbone; Introduce the operation (operation (II-2) and (III-1)) of amido acid structure; Has the operation (operation (I), (V-1), (V-2)) of the organic backbone of imide key with formation.In the operation that forms siloxane backbone, thereby be hydrolyzed and polycondensation formation siloxane bond, will the production method (IV) (hydrolysis and polycondensation step (IV)) as an example be described.
In aforementioned production method (IV), preferably carry out the hydrolysis and the polycondensation of following structural unit, but described structural unit be by make at least one organic backbone with imide key individually with the monomer (monomer M with structure that hydrolyzable wherein and polycondensation group be connected with Siliciumatom
1) in conjunction with or simultaneously also with another monomer (monomer M
2) in conjunction with and obtain.In fact monomer M
1Be preferably the monomer that limits by following general formula:
XfZhY
1gSi
In this formula, X and Z indication are same as described above; Y
1The expression hydrolysable group; F and g can be identical or different, the integer of expression 1~3; H is 0~2 integer; And f+g+h=4.In fact, preferred examples is as follows.
Organosilane monomer M
2Be preferably the monomer that limits by following general formula:
ZkY
1jSi
In this formula, Y
1Same as described above with the Z indication; K represents 0~3 integer; J is 1~4 integer; And k+j=4.In addition, in above-mentioned monomer M
1And M
2In, Y
1Be preferably described atom of above-mentioned Y and group.
As mentioned above, owing to used two or more monomers (must comprise monomer M
1), so can produce the silane compound with the polysiloxane skeleton that comprises following structural unit, described structural unit is by making at least one derived from monomer M
1The organic group with imide key be connected with Siliciumatom and form (in two or more monomer M
1In the situation of cocondensation, for having the silane compound of the polysiloxane skeleton that contains this cocondensation composition).Can also produce the silane compound of the polysiloxane skeleton with following formation, described polysiloxane skeleton is by making at least one derived from monomer M
1The organic group with imide key be connected in Siliciumatom and the structural unit that forms with by making derived from monomer M
2Any organic group be connected in Siliciumatom and the structural unit that forms connects or form with the copolymerization of wherein not having the structural unit that organic group is connected with Siliciumatom.
By with the identical mode of aforementioned production method (IV), also the silane compound that above-mentioned formula (9) can be limited and another silane compound monomer that does not have amido bond in production process (II-1) thus in cohydrolysis and condensation obtain intermediate (8) as the various combinations that comprise various structural units of silane compound, and with described intermediate (8) thus imidization acquisition silane compound (1).
Similarly, equally in production process (III-2), silane compound and another silane compound monomer cohydrolysis and the condensation that above-mentioned formula (13) can be limited, and then carry out production process (II-2) and production process (I) in succession, thereby obtain to have the silane compound of polysiloxane skeleton, described polysiloxane skeleton can have the various compositions that must comprise the structural unit that makes the organic backbone with imide key be connected at least one Siliciumatom and form.
Can suitably select aforementioned production method (for example embodiment (A)~(D)) according to the silane compound that desire obtains.The silane compound of Huo Deing can be preferred for such use by the way, and also is one of preferred implementation of the present invention by the silane compound that aforementioned production method is produced.For example, this silane compound is equally preferably by making organosilane monomer M
1Separately cohydrolysis and condensation and the multipolymer that obtains (comprises homopolymer and two or more organosilane monomer M
1Co-condensation polymer) or make organosilane monomer M
1Silicon monomer M with the hydrolyzable condensation that does not contain organic skeleton X
2The multipolymer that carries out cohydrolysis and condensation jointly and obtain is formed, described monomer M
1By make at least one organic backbone and Siliciumatom with imide key in conjunction with and the group (be also referred to as hydrolysable group: for example alkoxyl group, hydrogen atom, halogen atom and hydroxyl) that makes at least one hydrolyzable and/or can form siloxane bond be connected with same Siliciumatom and obtain.
Following compound is preferably as above-mentioned silicon monomer M
2
Tetraalkoxysilane, for example tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, tetraisobutoxy-silicane alkane, four sec-butoxy silane and four tert.-butoxy silane; Trialkoxy silane, methyltrimethoxy silane for example, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the sec.-propyl Trimethoxy silane, the sec.-propyl triethoxyl silane, 3,3,3-trifluoro propyl Trimethoxy silane, 3,3,3-trifluoro propyl triethoxyl silane, 3-sulfydryl propyl trimethoxy silicane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, phenyltrimethoxysila,e, phenyl triethoxysilane, the phenmethyl Trimethoxy silane, the phenmethyl triethoxyl silane, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane and 3-(methyl) acryloxy propyl-triethoxysilicane; Dialkoxy silicane, for example dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, diethyl diethoxy silane, di dimethoxy silane, di diethoxy silane, diisopropyl dimethoxy silane, di-isopropyl diethoxy silane, dimethoxydiphenylsilane and phenylbenzene diethoxy silane; Four acyloxy silanes, for example tetrem acyloxy silane and four propionyloxy silane; Three acyloxy silanes, for example methyl triacetoxysilane and ethyl triacetoxysilane; With two acyloxy silanes, for example dimethyl diacetoxy silane and diethyl diacetoxy silane.Among these silane, preferred tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, dimethyldimethoxysil,ne, dimethyldiethoxysilane.As mentioned above, preferably comprise alkoxyl silicone.In addition, trialkoxy silane is preferably as each M
1And M
2
Equally preferably produce above-mentioned silane compound (above-mentioned silane compound (i) or the silane compound (1) that limits by above-mentioned general formula (1)) with cage type molecular structure by aforementioned production method (aforementioned production method (I), (II), (III), (IV) and (V)), more specifically, more preferably produce described compound by aforesaid method (III) or aforesaid method (IV).In this case, the compound that preferably formula (13) is limited is as the parent material in the aforesaid method (III).In addition, the compound that preferably formula (11) is limited is as the parent material in the aforesaid method (IV).
Can be by for example reference 1 (F.J.Feher and K.D.Wyndham, Chem.Comm., 1998,323-324) building-up process described in uses the compound that is limited by following formula (g) to produce the compound with cage type molecular structure that is limited by formula (13) or formula (11) as initial substance.
NH
2-R
1-SiX
3????(g)
In this formula, R
1Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring; X can be identical or different, expression hydrolysable group or hydroxyl; Wherein said hydrolysable group is hydrogen atom, halogen atom, alkoxyl group or acyloxy.
An example that has shown the production method of the silane compound by using the initial substance that limits by above-mentioned formula (g) to obtain to have the cage type molecular structure in the following formula, however described method specifically is not limited to this embodiment.
To be described above-mentioned formula.
Obtain to have the silane compound means (iv) of trapezoidal amido acid structure for the compound that limits by above-mentioned formula (g), have two kinds of processes to enumerate as initial substance; A kind of is via having the process that NH3+ ionic compound (gegenion is any ion) obtains described silane compound (obtaining (ii) operation by (i) in the formula), and another kind is the process that obtains described silane compound via having amino compound (obtaining (iii) operation by (i) in the formula).
In this formula, obtaining (ii) operation by (i) is to be hydrolyzed in the presence of hydrochloric acid operation with condensation reaction of the compound that formula (g) limits, in addition, be that the compound that formula (g) limits is hydrolyzed and the operation of condensation reaction by (i) to (iii) operation.
By these operations, can obtain not have silanol group and as (ii) or the compound that is (iii) limited.Described compound is corresponding to the above-claimed cpd with cage type molecular structure that is limited by formula (13) or (11).
Afterwards, compound is (ii) or (iii) by opening and acid anhydrides (i.e. 5-norbornylene-2 in this formula, 3-dicarboxylic anhydride) reaction, thereby obtained as the cagelike silsesquioxane with amido acid structure that (iv) limits (iv).
And then, compound is (iv) dewatered and cyclization, thereby obtain as (the v) cagelike silsesquioxane with imide key of Xian Dinging.
The present invention still comprises the resin combination of above-mentioned silane compound (above-mentioned silane compound (i) or the above-mentioned silane compound (1) that is limited by formula (1)) and organic resin.Described resin combination is the composition that comprises the silane compound that is mixed with polymkeric substance, because described composition contains described silane compound, cause hardly also under the high temperature that weight reduces or the deterioration of mechanical-physical aspect even described composition exhibiting goes out excellent thermotolerance and is positioned over for a long time, thereby especially can be used for having the installation material of high heat resistance.In addition, described composition not only can be used for the installing area of requirement high thermal stability, also can be used for optical applications, optical device purposes, display equipment purposes, mechanical part, Electrical and Electronic component materials, trolley part material, civil engineering work and material of construction, formed material and coating and tackiness agent material.
For particularly preferred purposes, described composition can be preferred for semiconductor-encapsulating material, liquid sealing material, underfill (under fill), light-emitting device transparent sealant, passivation, semiconductor mounting substrate, solder resist, lead frame tackiness agent, semiconductor stratification binder film and semi-conductor installation processing of films (as chip attachment film (DAF)/polished backside film (BG)/dicing tape (DC)) etc.In addition, described composition also is preferred for semi-conductor purposes (semiconductor device purposes) is installed.The example of described purposes comprises: the conducting paste tackiness agent; Use tackiness agent with the CCL that comprises Copper Foil and flexible membrane (copper clad laminate), described flexible membrane for example has crystallinity polyester such as polyimide and PEN (poly-naphthalene diacid second diester) and PEEK (the registrar name of an article, polyether-ether-ketone) etc.In addition, described composition is preferably used as bonded permanent magnet dielectric materials used in thermosetting adhesive resin combination or the semiconductor device etc.Corresponding to purposes as these semi-conductor installation partss (member for semiconductor device), there is material with various mechanical-physical character from softness to high rigid nature, use resin combination of the present invention and can obtain high-insulativity, agent of low hygroscopicity, high heat resistance and binding property, thereby described resin combination can play a role in any component form effectively.As described, semiconductor device is one of preferred implementation of the present invention with the embodiment of resin combination (semi-conductor is installed and used resin combination).Particularly, present invention includes semiconductor-encapsulating material and the semiconductor mounting substrate that uses above-mentioned semiconductor device to use resin combination.Described resin combination also preferably is used as the resin combination of the binder layer that forms semi-conductor installation processing of films.
The silane compound (1) that is included in silane compound in the above-mentioned resin combination and can is above-mentioned silane compound (i) or limited by above-mentioned formula (1), preferred silane compound as mentioned above.
In addition, form the resin combination that semi-conductor is installed the binder layer of processing of films, then preferably suitably select above-mentioned silane compound according to the character of organic resin if above-mentioned resin combination is used as.
For example, be to have in the situation of resin of high hydrophobicity at organic resin, the X in above-mentioned silane compound in the preferably above-mentioned average group accepted way of doing sth is limited by following formula (A):
In this formula, R
1 ', R
2 ', R
3 'And R
4 'Can be identical or different, represent hydrogen atom or organic group, and can interconnect, wherein R
1 'And R
4 'In one be the non-aromatic organic group.R more preferably
1 'And/or R
4 'Be alicyclic hydrocarbon radical or aliphatic chain alkyl.This structure comprises wherein R
1 'And R
3 'Thereby interconnect the structure that forms as the ring structure of alicyclic structure.R further preferably
1 'And/or R
4 'Be the aliphatic chain alkyl, and then the group that more preferably limits by following formula:
-CH
2-CH(CH
3)=CH-R
5’
In this formula, R
5 'The alkyl of 4~8 carbon atoms of expression.
At described organic resin is to have under the situation of high polar resin, R preferably in the above-mentioned silane compound that above-mentioned formula (A) limits
1 'And R
3 'Thereby interconnect the ring structure that forms as aromatic ring structure.And, there is not R in this case
1 'And R
4 '
If R
1 '~R
4 'In at least one is the silane compound that contains succinimide group (being thiazolinyl), then especially preferably use hydrophobic grouping, as polyolefine and silicon.In view of the above, can improve thermotolerance and anti-water absorbability simultaneously, and not reduce binding property.Described resin combination can be preferably used as installation such as chip attachment film (DAF), polished backside film (BG) and dicing tape semi-conductive tackiness agents such as (DC) especially.
Resin combination of the present invention comprises organic resin, described organic resin is preferably compound, polyphenolic substance and the maleimide compound that has glycidyl and/or epoxy group(ing) at least, and these compounds can use separately, also can be with being used in combination in them.As described, above-mentioned resin combination can be the resin combination (being also referred to as resin combination (1)) that comprises the compound that has glycidyl and/or epoxy group(ing) at least, the resin combination (being also referred to as resin combination (2)) that comprises polyphenolic substance and the resin combination (being also referred to as resin combination (3)) that comprises maleimide compound, and these resin combinations also are preferred implementations of the present invention.
In addition, described organic resin is except comprising above-mentioned resin, also preferably include thermoplastic resin, for example (modification) polythylene resin, (modification) polypropylene-based resin, the ABS resinoid, the AES resinoid, AAS resin, methacrylic resin, polystyrene resins, polyamide-based resin (comprising polyamide thermoplastic class elastomerics), thermoplastic polyurethanes resin (comprising the thermoplastic polyurethanes elastomerics), the polyacetals resin, the polyphenylene oxide resinoid, the modified polyphenyl ether resin, polycarbonate resin, polyester resin (comprising thermoplastic polyester class elastomerics), the polysulfones resin, the polyether sulfone resin, the polyphenylene sulfide resinoid, the polyacrylic ester resinoid, the polyetherketone resinoid, the polyetherketone resinoid, polyimide based resin, polyetherimide resinoid and polyamideimides resin; And thermosetting resin, for example melamine resin, guanamine resin, urea resin, xylene resin, urethane resin, Synolac, unsaturated polyester resin, epoxy (methyl) acrylate resin, vinyl ether resin, bismaleimides-cyanate resin and polyaniline resin.If as thermosetting resin, the silane compound of the imide propyl group that then preferably will contain is dissolved in and comprises epoxy group(ing), glycidyl, phenolic group, contains in the imide group of unsaturated double-bond in any organic resin with described resin combination.In view of the above, can further improve thermotolerance, anti-water absorbability, low dielectric characteristics.Thereby described resin combination is preferably used as thermosetting resin especially.
Below, description is preferred for the compound that has epoxy and/or glycidyl at least, polyphenolic substance, the maleimide compound of organic resin of the present invention and the resin combination that comprises these compounds.
The described compound that has epoxy and/or glycidyl at least is preferably following compound.Example has: by showing the polymer scale pair class glycidyl ether epoxy that two class (epibis-type) glycidyl ester epoxy resins (by the condensation reaction with epihalohydrin obtains such as bis-phenols such as dihydroxyphenyl propane, Bisphenol F, bisphenol Ss) and the above-mentioned addition reaction such as bis-phenols such as dihydroxyphenyl propane, Bisphenol F, bisphenol Ss obtain; Novolac aralkyl class glycidyl ether epoxy, condensation reaction by polyphenol and epihalohydrin obtains, and described polyphenol is obtained by the condensation reaction of phenol (such as phenol, cresols, xylenol, naphthols, Resorcinol, pyrocatechol, dihydroxyphenyl propane, Bisphenol F, bisphenol S) with formaldehyde, acetaldehyde, propionic aldehyde, phenyl aldehyde, hydroxy benzaldehyde, salicylic aldehyde, dicyclopentadiene, terpene, tonka bean camphor, p-Xylol glycol dimethyl ether, dichloro-p-xylene and two (methylol) biphenyl; The aromatic series crystallinity Resins, epoxy that condensation reaction by tetramethyl-bis-phenol, tetramethyl-Bisphenol F, quinhydrones, naphthalene glycol and epihalohydrin obtains; The high-molecular weight polymer of the aromatic series crystallinity Resins, epoxy that obtains with further addition reaction by above-mentioned bis-phenol and tetramethyl-bis-phenol, tetramethyl-Bisphenol F, quinhydrones, naphthalene glycol; By alicyclic diol (by to above-mentioned bis-phenol and tetramethyl-bis-phenol, the tetramethyl-Bisphenol F, quinhydrones, the aromatic series skeleton of naphthalene glycol carries out hydrogenation and obtains) and ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, PEG 600, propylene glycol, dipropylene glycol, tripropylene glycol, four propylene glycol, polypropylene glycol, PPG, glycerine, two glycerine, four glycerine, Polyglycerine, TriMethylolPropane(TMP) and polymkeric substance thereof, tetramethylolmethane and polymkeric substance thereof, monose/polysaccharide is (as glucose, fructose, lactose and maltose) the aliphatic glycidyl base ethers Resins, epoxy that obtains with the condensation reaction of epihalohydrin; As 3 ', 4 '-epoxycyclohexyl carboxylic acid (3, the 4-epoxy cyclohexane) methyl ester etc. has the Resins, epoxy of the skeleton of epoxy cyclohexane; The glycidyl esters based epoxy resin that condensation reaction by tetrahydrophthalic acid, hexahydro-phthalic acid, phenylformic acid and epihalohydrin obtains; At room temperature be the glycidyl ether based epoxy resin that contains tertiary amine of solid phase with condensation reaction by glycolylurea, tricyanic acid, trimeric cyanamide and benzo guanamine etc. and epihalohydrin obtains.Appearance degradation when especially, above-mentioned aliphatic glycidyl base ethers Resins, epoxy and Resins, epoxy with epoxy cyclohexane skeleton more preferably are used to suppress rayed.
In resin combination (1), with the gross weight of organic resin and silane compound (if used solidifying agent, then for the gross weight of organic resin, silane compound and solidifying agent) be made as under the situation of 100 weight %, the lower limit of the content of above-mentioned silane compound is preferably 3 weight %, more preferably 10 weight %, and then more preferably 15 weight %.The upper limit is preferably 80 weight %, more preferably 70 weight %, and then more preferably 60 weight %.
Content for the compound that comprises glycidyl and/or epoxy group(ing) in the resin combination (1), with the gross weight of organic resin and silane compound (if used solidifying agent, then be the gross weight of organic resin, silane compound and solidifying agent) be made as under the situation of 100 weight %, lower limit is preferably 10 weight %, more preferably 20 weight % and then more preferably 30 weight %.The upper limit is preferably 95 weight %, more preferably 90 weight % and then more preferably 85 weight %.
For the epoxy equivalent (weight) in the above-mentioned resin combination (1), lower limit is preferably 100g/mol, more preferably 120g/mol and then more preferably 150g/mol.The upper limit is preferably 450g/mol, more preferably 420g/mol and then more preferably 400g/mol.
For the viscosity of above-mentioned resin combination (1) 25 ℃ or 60 ℃, lower limit is preferably 1200mPas, more preferably 1500mPas and then more preferably 1800mPas.The upper limit is preferably 4200mPas, more preferably 4000mPas and then more preferably 3800mPas.
Thermal softening temperature, lower limit for above-mentioned resin combination (1) are preferably 45 ℃, more preferably 70 ℃.The upper limit is preferably 200 ℃, more preferably 150 ℃.
For fusing point, lower limit is preferably 80 ℃, more preferably 100 ℃.The upper limit is preferably 300 ℃, more preferably 250 ℃.
Above-mentioned resin combination can also contain additive except above-mentioned element, for example stablizer, releasing agent, coupling agent, tinting material, softening agent, as thinners such as reaction diluent, softening agents, various rubber-like material, sensitization sensitizer, filler, fire retardant and pigment.
Above-mentioned resin combination (1) can be by obtaining solidifying article with the solidifying agent thermofixation.
Above-mentioned solidifying agent can be one or more compounds, and for example, acid anhydrides is as methyltetrahydro Tetra hydro Phthalic anhydride, hexahydro phthalic anhydride, dehydration methylhexahydrophthalic acid, PMA and methyl Na Dike acid; Various phenol resins, for example phenol novolac resin, cresols novolac resin, bisphenol-A phenolic varnish resin, dicyclopentadiene phenol resins, phenol aralkyl resin and terpene-phenolic resin; Various phenol resins are for example by various phenol and the polyphenol resin that obtains such as the condensation reaction of hydroxy benzaldehyde, crotonic aldehyde and oxalic dialdehyde etc. various aldehyde; BF
3Complex compound, sulfonium salt and imidazoles.
For above-mentioned curing, can use curing catalyst, for example be preferably one or more organo phosphorous compoundss, as triphenylphosphine, bromination tributyl Shi Liu Wan Ji Phosphonium, tributylphosphine and three (Dimethoxyphenyl) phosphine.
Above-mentioned solidified temperature is preferably 70 ℃~200 ℃, more preferably 80~150 ℃.Be preferably 1 hour set time~15 hours, more preferably 5 hours~10 hours.
The example of the curing article that can obtain in the above described manner has formed bodys such as article, film, sheet material and the pellet such as random shape, and the curing article that utilize resin combination of the present invention (1) to obtain are one of preferred implementations of the present invention.The resin combination that can be cured (1) is also referred to as curable resin composition (1).
Above-mentioned resin combination (1) can be preferred for, for example, and component materials, civil engineering work and material of construction, formed material and the coating of mechanical part material, Electrical and Electronic component materials, vehicle, boats and ships and aircraft and tackiness agent material.In fact, described composition can be preferred for printed circuit board (PCB), stack-up type running board, solder resist, laminated plates, with material, as fiber-reinforced plastic material, injecting forming material, tackiness agent and the electrical insulating coating relevant with civil engineering work raw materials such as (FRP), the semiconductor device or the printed circuit board (PCB) that comprise the curing article of resin combination (1) also are one of preferred implementations of the present invention to photodiode (LED) with material, liquid-crystal display and Organnic electroluminescent device (organic EL) sealing material, semiconductor device.
Description is suitable for polyphenol as organic resin contained in the resin combination of the present invention (2) (being also referred to as flame retardant resin composition).The example that can be preferably used as above-mentioned polyphenolic substance is to have that the aromatic series skeleton that will have at least one phenolic hydroxyl group via the organic backbone with 2 above carbon atoms connects and the compound of the structure that forms.In above-mentioned polyphenolic substance, described aromatic series skeleton is the aromatic nucleus with at least one phenolic hydroxyl group.Described aromatic series skeleton is the part with phenols structure, and preferred phenol, hydroquinones, aphthols, anthrol class, bisphenols and '-biphenyl diphenol class.Especially, preferred phenol.In addition, described part with phenols structure can suitably be substituted with alkyl, alkylidene group, aralkyl, phenyl and phenylene.
In above-mentioned polyphenolic substance, described organic backbone is meant the part of the aromatic nucleus skeleton that must comprise carbon atom and connect to form polyphenolic substance.In addition, described organic backbone with 2 above carbon atoms preferably has ring structure.Described ring structure is meant the structure that has such as rings such as alicyclic ring and aromatic nucleus, and preferred ring has pentamethylene ring, cyclohexane ring, phenyl ring, naphthalene nucleus and anthracene nucleus.In addition, described organic backbone for example has preferably that triazine ring and phosphine nitrile ring etc. comprise the ring structure and/or the aromatic nucleus of nitrogen-atoms, and then more preferably has triazine ring and/or aromatic nucleus.Described polyphenolic substance can have another aromatic series skeleton and and the organic backbone except that above-mentioned organic backbone, and can have the structure that the organic backbone (methylene radical) of aromatic series skeleton through having 1 carbon atom that has at least one phenolic hydroxyl group is separately connected and form simultaneously.
Have in the situation of ring structure as organic backbone that comprises nitrogen-atoms at above-mentioned polyphenolic substance, described compound preferably has the nitrogen atom content of 1 weight %~50 weight %.If it is less than 1 weight %, then electronic material may become not enough with the flame retardant resistance of formed material, tackiness agent and coating, if it surpasses 50 weight %, then may become is difficult to satisfy simultaneously physical properties and flame retardant resistance.It is 3 weight %~30 weight % more preferably, and then 5 weight %~20 weight % more preferably.Nitrogen atom content is meant in the weight with polyphenolic substance and is made as the weight ratio of forming the nitrogen-atoms of this polyphenolic substance under the situation of 100 weight %.
Can be used for polyphenolic substance of the present invention and be preferably the compound of producing by the reaction raw materials that must comprise compound (hereinafter being also referred to as the compound that forms the aromatic series skeleton) that forms aromatic series skeleton and the compound (hereinafter being also referred to as the compound that forms organic backbone) that forms organic backbone with 2 above carbon atoms with at least one phenolic hydroxyl group.
Above-mentioned reaction raw materials is meant and contains the compound that forms the aromatic series skeleton and the compound that forms organic backbone as the neccessary composition and the optional mixture of the solvent that reacts of other compound and being used to alternatively.One or more compounds can be respectively applied for and form the aromatic series skeleton and form organic backbone.
The above-mentioned compound that is used to form the aromatic series skeleton can be the substituent compound that comprises outside aromatic nucleus and one or more phenolic hydroxyl group and the optional one or more hydroxyl-removal.The above-mentioned examples for compounds that is used to form the aromatic series skeleton is preferably phenol, ortho-cresol, meta-cresol, p-cresol, phlorol, p-ethyl phenol, cresols, to hydroxyethyl phenol, align propylphenol, o-isopropyl phenol, australol, mix isopropyl-phenol, o-sec-butyl phenol, between tert.-butyl phenol, p-tert-butylphenol, amyl phenol, paraoctyl phenol, to nonylphenol, 2, the 3-xylenol, 2, the 4-xylenol, 2, the 6-xylenol, 3, the 4-xylenol, 2, the 4-di sec-butylphenol, 3, the 5-xylenol, 2, the 6-di sec-butylphenol, 2,6 di t butyl phenol, 3 methyl 4 isopropyl phenol, 3-methyl-5-isopropyl-phenol, 3-methyl-6-isopropyl-phenol, the 2-tertiary butyl-4-methylphenol, 3 methy 6 tert butyl phenol and the 2-tertiary butyl-4-ethylphenol.Examples for compounds with 2 above phenolic hydroxyl groups is preferably pyrocatechol, Resorcinol, '-biphenyl diphenol, dihydroxyphenyl propane, bisphenol S and Bisphenol F, and is preferably the compound that forms the Ppolynuclear aromatic skeleton, as naphthyl alcohol and 2-Naphthol.
The compound of above-mentioned formation organic backbone is preferably aromatics that (1) have Alpha-hydroxy alkyl, alpha-alkoxy base alkyl or α-acetoxyl group alkyl, compound that (2) have unsaturated link(age), compound that (3) have carbonyl, and for example aldehyde and ketone, (4) have the compound of two or more described given activity groups or active part and (5) and have amino, hydroxyalkyl is amino or two (hydroxyalkyls) are amino compound.
The example of above-mentioned aromatics (1) is preferably terephthalyl alcohol, the terephthalyl alcohol dimethyl ether, to the diacetoxy methylbenzene, isophthalic alcohol, the isophthalic alcohol dimethyl ether, between the diacetoxy methylbenzene, to the dihydroxyl isopropyl benzene, to the dimethoxy isopropyl benzene, to the diacetoxy isopropyl benzene, trishydroxymethyl benzene, the trihydroxy-isopropyl benzene, the trimethoxy methylbenzene, the trimethoxy isopropyl benzene, 4,4 '-hydroxymethyl biphenyl, 4,4 '-methoxymethyl biphenyl, 4,4 '-acetoxy-methyl biphenyl, 3,3 '-hydroxymethyl biphenyl, 3,3 '-methoxymethyl biphenyl, 3,3 '-acetoxy-methyl biphenyl, 4,4 '-hydroxyl isopropyl biphenyl, 4,4 '-methoxyl group isopropyl biphenyl, 4,4 '-acetoxyl group isopropyl biphenyl, 3,3 '-hydroxyl isopropyl biphenyl, 3,3 '-methoxyl group isopropyl biphenyl, 3,3 '-acetoxyl group isopropyl biphenyl, 2,5-methylol naphthalene, 2,5-methoxymethyl naphthalene, 2,5-acetoxy-methyl naphthalene, 2,6-methylol naphthalene, 2,6-methoxymethyl naphthalene, 2,6-acetoxy-methyl naphthalene, 2,5-hydroxyl isopropyl naphthalene, 2,5-methoxyl group isopropyl naphthalene, 2,5-acetoxyl group isopropyl naphthalene, 2,6-hydroxyl isopropyl naphthalene, 2,6-methoxyl group isopropyl naphthalene and 2,6-acetoxyl group isopropyl naphthalene.
Above-mentioned example with compound (2) of unsaturated link(age) is preferably Vinylstyrene, di isopropenylbenzene, trivinylbenzene, three isopropenylbenzenes, dicyclopentadiene, norbornylene and terpene.Above-mentioned example with compound (3) of carbonyl be preferably various aldehyde with 5~15 carbon atoms and ketone and phenyl aldehyde, octanal, pimelinketone, methyl phenyl ketone, hydroxy benzaldehyde, hydroxy acetophenone, crotonic aldehyde, phenylacrolein, oxalic dialdehyde, glutaraldehyde, terephthalaldehyde, hexanaphthene dicarbaldehyde, tristane dicarbaldehyde, norbornane dicarbaldehyde and suberic aldehyde (suberaldehyde).
In having the compound (4) of two or more given activity groups or active part, the compound with carbonyl and unsaturated link(age) is preferably pseudoallyl phenyl aldehyde, pseudoallyl methyl phenyl ketone, geranial, citral and perylene aldehyde (perylaldehyde).In addition, the compound with Alpha-hydroxy alkyl or alpha-alkoxy base alkyl and unsaturated link(age) is dihydroxymethyl vinylbenzene, dihydroxymethyl-alpha-methyl styrene, dimethoxy-methyl vinylbenzene, dimethoxy-methyl-alpha-methyl styrene, methylol Vinylstyrene, methylol diisopropyl benzene, methoxymethyl Vinylstyrene and methoxymethyl diisopropyl benzene.
Has amino, the example of the compound (5) that hydroxyalkyl amino or two (hydroxyalkyls) are amino is trimeric cyanamide preferably, the dihydroxymethyl trimeric cyanamide, trimethylol melamine, acetylguanamine, the dihydroxymethyl acetylguanamine, the tetra methylol acetylguanamine, benzo guanamine, the dihydroxymethyl benzo guanamine, the tetra methylol benzo guanamine, urea, dihydroxymethyl urea, tetra methylol urea, quadrol, the dihydroxymethyl quadrol, the tetra methylol quadrol, six ethylene diamines, dihydroxymethyl six ethylene diamines, tetra methylol six ethylene diamines, the p-Xylol diamines, to the dihydroxymethyl amino-benzene, m-xylene diamine, between the dihydroxymethyl amino-benzene, 4,4 '-methylene dianiline (MDA) and 4,4 '-methylene radical dihydroxymethyl aniline.The compound that preferably has the triazine skeleton among them, for example trimeric cyanamide, benzo guanamine and acetylguanamine.
Above-mentioned reaction raw materials preferably includes the compound (hereinafter being also referred to as raw material A) that forms the aromatic series skeleton and the compound (hereinafter being also referred to as raw material B) that is selected from least one organic backbone of formation in above-claimed cpd (1)~(5) as neccessary composition, more preferably comprises raw material A, the compound (5) (hereinafter being also referred to as raw material B2) of the compound (hereinafter being also referred to as raw material B1) of at least one organic backbone of formation in (1)~(4) that are selected from above-claimed cpd and at least one organic backbone of formation is as neccessary composition.Reaction sequence for reaction raw materials in this situation, preferably before beginning reaction, be pre-mixed raw material A, raw material B1 and raw material B2, with finish in the reaction of raw material A and raw material B1 before cause the reaction of raw material B2, for example, raw material A, raw material B 1 and raw material B2 are reacted simultaneously, or raw material A and raw material B2 were reacted in the fs, raw material B1 is further reacted in subordinate phase.Therefore, flame retardant resistance is improved conscientiously, and the product that is obtained more preferably is suitable for electronic material formed material, tackiness agent and coating.More preferably after the fs makes raw material A and raw material B2 reaction, raw material B1 is further reacted in subordinate phase.
Used raw material A and the mixing mol ratio of raw material B are preferably 1/1~10/1 in producing the situation of above-mentioned polyphenolic substance.If raw material A is less than 1/1, when producing resin combination of the present invention gelation can take place, if raw material A more than 10/1, may be difficult to show the flame retardant resistance of this resin combination.This ratio more preferably 1.3/1~8/1 is because described resin combination at high temperature can show high strength.This ratio and then more preferably and 1.8/1~5/1.
Preferably in the presence of catalyzer, produce above-mentioned polyphenolic substance by the reaction of above-mentioned reaction raw materials.The catalyzer that can be used for producing described polyphenolic substance can be any catalyzer, as long as it can promote the catalyst for reaction of above-mentioned reaction raw materials.Use in the situation of catalyzer in the reaction of raw material B1, preferred catalyst as acid catalyst is mineral acid and organic sulfonic acid, for example hydrochloric acid, sulfuric acid, phosphoric acid, tosic acid and methylsulfonic acid, super acids, for example boron trifluoride and complex compound thereof, trifluoromethanesulfonic acid, heteropolyacid, alukalin, solid acid catalyst, for example alukalin, synthetic zeolite, sulfonic acid class ion exchange resin and perfluoro alkane sulfonic acid class ion exchange resin.In the situation of the reaction of above-mentioned raw materials B1, can suitably set catalyst consumption according to corresponding strength of acid, yet with respect to the consumption of raw material B1, it is preferably 0.001 weight %~100 weight %.For the catalyzer that is used for the homogeneous system in the above-mentioned scope, preferred trifluoromethanesulfonic acid, methylsulfonic acid and boron trifluoride, and these catalyst consumption are preferably 0.001 weight %~5 weight %.The ion exchange resin of nonhomogeneous system and the consumption of alukalin are preferably 1 weight %~100 weight %.
Use in the situation of above-mentioned catalyzer in the reaction of raw material B2, the example of basic catalyst is preferably for example oxyhydroxide and oxide compound, ammonia, primary amine~tertiary amine, vulkacit H and the yellow soda ash of basic metal such as sodium hydroxide, potassium hydroxide and hydrated barta and alkaline-earth metal, the example of acid catalyst has: mineral acid, example hydrochloric acid, sulfuric acid and sulfonic acid, organic acid, as oxalic acid and acetate, and divalent metal salt basic catalyst, as Lewis acid and zinc acetate.Resin combination of the present invention is being used in the situation of epoxy curing agent as the Electrical and Electronic material, since such as inorganicss such as metal residual for relict catalyst be not preferred, preferably use amine as basic catalyst with use organic acid as an acidic catalyst.
In addition, if desired, after the reaction of raw material B2, preferably by neutralization and the washing impurity such as desalination of making a return journey.In addition, using under the situation of amine as catalyzer, preferably do not wait the removal of carrying out impurity by neutralization or washing.
Can obtain above-mentioned polyphenolic substance by the aromatic nucleus of raw material A and the substituent condensation of raw material B, at this moment, carboxylic acid, alcohol and water etc. generates with described polyphenolic substance as by product.Can be by between the reaction period or the underpressure distillation after the reaction or the carboxylic acid, the alcohol and water that generate as by product are easily removed from reaction product with the azeotropic of solvent, and do not need complicated step.Reaction product is meant the mixture that contains all substances that generated by above-mentioned reaction, the catalyzer that contains polyphenolic substance, the carboxylic acid as the by product generation, alcohol and water and use in case of necessity, the solvent that will be described below in addition.
Reaction conditions for the production of above-mentioned polyphenolic substance, but temperature of reaction preferably is adjusted to evaporative removal as the carboxylic acid of by product generation, the temperature of alcohol and water, and is preferably 100 ℃~240 ℃, more preferably 110 ℃~180 ℃ and then more preferably 130 ℃~160 ℃.As described, in the production of polyphenolic substance, carboxylic acid etc. generate as by product, yet, can easily it be removed from reaction product.Though the reaction times is depended on the type of used raw material, catalyzer and the amount and the temperature of reaction of catalyzer, but the reaction times is preferably when the reaction of raw material A and raw material B is finished basically, promptly when regeneration carboxylic acid not, alcohol or water, thereby its be preferably 30 minutes~24 hours, more preferably 1 hour~12 hours.
For the reaction method in the production of above-mentioned polyphenolic substance, can in the presence of solvent, carry out described reaction, as solvent, preferably use the organic solvent of non-activity in the reaction of raw material A and raw material B, can use toluene, dimethylbenzene, monochloro-benzene and dichlorobenzene etc.The use of solvent can make raw material be dissolved in wherein and evenly.For the reaction of raw material B1, preferably when not existing, solvent reacts.
In the situation of producing above-mentioned polyphenolic substance, when by products such as carboxylic acid, alcohol and water are removed from reaction product, preferably by under the decompression of 0.1kPa~10kPa, distilling they removals in said temperature.At this moment, because unreacted phenol may be distilled, therefore preferably after finishing basically, reaction carries out described removal.
Resin combination of the present invention (resin combination (2)) preferably contains the silane compound that is scattered in the organic resin, and described composition manufacturing method is preferably after producing described organic resin and above-mentioned silane compound respectively they blended methods.
For above-mentioned resin combination (2), the silane compound that preferably under the gross weight (if used solidifying agent, then being the gross weight of organic resin, silane compound and solidifying agent) with organic resin and silane compound is set at the situation of 100 weight %, in resin combination (2), contains the amount of 3 weight %~80 weight %.If less than 3 weight %, then possibly can't obtain excellent flame, if surpass 80 weight %, then may reduce the property handled and make the formability deterioration.It is 5 weight %~50 weight % more preferably.
For above-mentioned resin combination (2), with the gross weight of organic resin and silane compound (if used solidifying agent, then be the gross weight of organic resin, silane compound and solidifying agent) be made as under the situation of 100 weight %, the lower limit of the content of polyphenolic substance is preferably 10 weight %, more preferably 20 weight % and then more preferably 30 weight %.The upper limit is preferably 95 weight %, more preferably 90 weight % and then more preferably 85 weight %.
The thermal softening temperature of resin combination of the present invention (2) is preferably 45 ℃~200 ℃, more preferably 70 ℃~150 ℃.In addition, the hydroxyl value of above-mentioned resin combination (2) is preferably 100g/mol~280g/mol, more preferably 120g/mol~240g/mol.
When utilizing resin combination of the present invention (2) to prepare the curable resin composition of hereinafter describing (2), preferably use the composition of solution, varnish or thickener form sometimes.In this case, silane compound and polyphenol need be disperseed together and obtain good flowability.Resin combination (2) in this available embodiment preferably comprises and has one or more compounds that are selected from the structure in ehter bond, ester bond and the nitrogen-atoms at least as solvent, softening agent and lubricant.
Above-mentioned examples for compounds with ehter bond is preferably ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ether, hexyl ether, ethyl vinyl ether, butyl vinyl ether, phenylmethylether, phenyl ethyl ether, butyl phenylate, the amyl group phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, veratrole, propylene oxide, 1, the 2-butylene oxide ring, dioxane, three oxygen, six rings, furans, the 2-methyl furan, tetrahydrofuran (THF), tetrahydropyrans, Terpane, 1, the 2-glycol dimethyl ether, 1, the 2-diethoxyethane, 1,2-dibutoxy ethane, glyceryl ether, crown ether, methylal, acetal, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, the glycol monomethyl propyl ether, ethylene glycol mono hexyl ether, ethylene glycol dimethyl ether, Diethylene Glycol, the Diethylene Glycol methyl ether, the Diethylene Glycol ethyl ether, the Diethylene Glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the Diethylene Glycol dibutyl ether, triethylene glycol, the triethylene glycol monomethyl ether, TEG, 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, methyl proxitol, the propylene glycol dimethyl ether, the propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol, DPGME, dihydroxypropane single-ethyl ether, the dipropylene glycol dimethyl ether, the dipropylene glycol Anaesthetie Ether, the dipropylene glycol dibutyl ether, tripropylene glycol, the tripropylene glycol monomethyl ether, 2-methyl cellosolve, cellosolvo, 2-(methoxymethoxy) ethanol, the 2-isopropoxide ethanol, butoxy ethanol, 2-(isopentyloxy) ethanol, 2-(hexyloxy) ethanol, the 2-phenoxyethyl alcohol, 2-(benzyloxy) ethanol, furfuryl alcohol and tetrahydrofurfuryl alcohol.
Above-mentioned examples for compounds with ester bond is methyl-formiate preferably, ethyl formate, propyl formate, butyl formate, tetryl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, Isoamyl Acetate FCC, acetate 3-methoxyl group butyl ester, acetate Sec-Hexyl ester, acetate 2-ethyl butyl ester, acetate 2-ethylhexyl, ethyl cyclohexyl base ester, the acetate benzyl ester, methyl propionate, ethyl propionate, butyl propionate, isoamyl propionate, ethylene glycol acetate, the Diethylene Glycol monoacetate, glyceryl monoacetate, glyceryl diacetate, triacetin, glycerine only son acid esters (monobutylin), methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, butyric ester, isobutyrate, isopentanoate, stearate, benzoic ether, laurate, rosin ester, adipic acid ester, gamma-butyrolactone, barkite, malonic ester, maleic acid ester, tartrate, citrate, sebate, phthalic acid ester and oxalic acid second diester etc.
The above-mentioned examples for compounds that comprises nitrogen-atoms is Nitromethane 99Min., nitroethane, 1-nitropropane, 2-nitropropane, oil of mirbane, acetonitrile, propionitrile, sym-dicyanoethane, butyronitrile, isopropyl cyanide, valeronitrile, benzonitrile, α-benzyl nitrile, methane amide, N-methylformamide, N preferably, dinethylformamide, N, N-diethylformamide, ethanamide, N-methylacetamide, N, N-N,N-DIMETHYLACETAMIDE, N, N-diethyl acetamide, 2-Pyrrolidone, N-Methyl pyrrolidone and ε-Ji Neixianan etc.
Have multiple being selected from by ehter bond, the examples for compounds of the structure in the group that ester bond and nitrogen-atoms are formed is N-ethylmorpholine preferably, N-phenyl-morpholine, acetic acid methyl cellosolve, the acetate ethyl cellosolve, the acetate propyl cellosolve, the acetate ethylene glycol butyl ether, acetate phenoxy group ethyl ester, the diethylene glycol monomethyl ether acetic ester, the TC acetic ester, Diethylene Glycol list propyl ether acetic ester, Diethylene Glycol single-butyl ether acetic ester, methyl proxitol acetate, propylene glycol ethyl ether acetic ester, propylene glycol propyl ether acetic ester, the propylene glycol butyl ether acetic ester, the dipropylene glycol methyl ether acetic ester, dipropylene glycol ethyl ether acetic ester, dipropylene glycol propyl ether acetic ester, dipropylene glycol butyl ether acetic ester and tripropylene glycol methyl ether acetic ester etc.
With respect to the resin combination of 100 weight parts, have at least a consumption that is selected from the compound of the structure in the group of forming by ehter bond, ester bond and nitrogen-atoms and be preferably 5 weight parts~1000 weight parts.It is 10 weight parts~300 weight parts more preferably.
Resin combination of the present invention (2) can be used as the curable resin composition (solidified nature fire-proof resin composition) of semiconductor sealing material and running board usefulness insulating material when mixing with the compound with at least two glycidyls or other additive.Curable resin composition of the present invention is to contain above-mentioned polyphenolic substance, above-mentioned silane compound and have a compound compositions of at least two glycidyls, can obtain by above-mentioned composition that will contain polyphenolic substance and silane compound and method with compound of at least two glycidyls, also can perhaps mix obtaining with above-mentioned polyphenolic substance by with above-mentioned polyphenolic substance and above-mentioned silane compound while and compound with at least two glycidyls by the mixture that will be scattered in the silane compound in the compound with at least two glycidyls.As described, be used for semiconductor sealing material and the running board that comprises resin combination of the present invention (2) and have a compound of at least two glycidyls also is one of preferred implementation of the present invention with the curable resin composition of insulating material.
In addition, can make above-mentioned curable resin composition (2) form formed body by curing.In this way, by solidify formed body that curable resin composition of the present invention obtains, by sealing and solidify semiconductor device that semiconductor sealing material of the present invention obtains and by solidifying running board of the present invention with electricly being also contained among the preferred implementation of the present invention that insulating material obtains with running board.
Above-mentioned compound with at least two glycidyls is preferably the Resins, epoxy that on average has 2 above glycidyls in each molecule, and preference is: by as the table pair class glycidyl ether epoxy that obtain of the condensation reaction of bis-phenol such as dihydroxyphenyl propane, Bisphenol F and bisphenol S and epihalohydrin; The novolac resin aralkyl base class glycidyl ether epoxy that obtains by the condensation reaction of further carrying out polyphenol (obtaining) and epihalohydrin by reaction such as phenol such as phenol, cresols, xylenol, Resorcinol, pyrocatechol, dihydroxyphenyl propane and Bisphenol F and formaldehyde, acetaldehyde, propionic aldehyde, phenyl aldehyde, salicylic aldehyde, dicyclopentadiene, terpene, tonka bean camphor, p-Xylol dimethyl ether and dichloro-p-xylene; The glycidyl esters based epoxy resin that condensation reaction by tetrahydrophthalic acid, hexahydro-phthalic acid, phenylformic acid and epihalohydrin obtains; The glycidyl ether based epoxy resin that condensation reaction by A Hydrogenated Bisphenol A and glycol and epihalohydrin obtains; The glycidyl ether based epoxy resin that contains amine that condensation reaction by glycolylurea and cyanuric acid and epihalohydrin obtains; Encircle Resins, epoxy with aromatic series, as biphenyl based epoxy resin and naphthalene based epoxy resin more.Described examples for compounds can also comprise the compound that has epoxy group(ing) by the addition reaction of these Resins, epoxy and polyprotonic acid and/or bis-phenol in molecule.These compounds can use separately, also two or more compounds can be used in combination.
The mixed weight of above-mentioned resin combination (2) and Resins, epoxy is preferably 30/70~70/30 than (resin combination (2)/Resins, epoxy).If it is less than 30/70, the mechanical-physical character of then formed curing article etc. is easy to descend, if it surpasses 70/30, then flame retardant resistance may become not enough.It is more preferably 35/65~65/35 years old.
Said mixture can comprise other additive, and the example of other additive has curing catalyst, filler, coupling agent, fire retardant, softening agent, reaction diluent and pigment.
The preference of described curing catalyst has: imidazoles, as glyoxal ethyline and 2-ethyl-4-methylimidazole; Amine, as 2,4,6-three (dimethylaminomethyl) phenol, phenmethyl methylamine, DBU (1,8-diaza-bicyclo [5,4,0]-the 7-undecylene), (3-(3 for DCMU, the 4-dichlorophenyl)-1,1-dimethyl urea) and organo phosphorous compounds, as tributylphosphine, triphenylphosphine, three (Dimethoxyphenyl) phosphine.
In addition, as mentioned above, can be with above-mentioned resin combination (2) thus be in Resins, epoxy that solution, varnish or thickener etc. have mobile state mixes must forms such as ink, coating or varnish curable resin composition.In this case, after using as ink, coating or varnish, can will have at least a compound that is selected from the structure in the group of forming by ehter bond, ester bond and nitrogen-atoms by the drying under decompression and/or the heating and remove, thereby produce the rectangular products of making by resin combination (2).Can suitably adjust the drying conditions of ink and coating according to used at least a vapour pressure or the boiling point that is selected from the compound of the structure in the group of forming by ehter bond, ester bond and nitrogen-atoms that have.In the situation that varnish is used for flooding, can use fiber-reinforced material as objective body to be impregnated.
The above-mentioned strengthening material of available can be the strengthening material known to usually, example have N type, NE type, S type, T type, D type glass glass fibre weave cotton cloth or non-woven fabrics, as inorganic materials and organic materialss such as quartz.They can use with glass roving cloth, woven fiber glass, short form of cutting glass, hollow glass fibre, glass mat, glass surface felt, glass non woven fibre, ceramic fiber spun product (fabric etc.) and steel fiber textiles.In addition, can use such as synthetic organic reinforcement fillers such as the organic polymers that can form fiber for the present invention.The typical example of strengthening with organic fibre has poly-(ether ketone), polyimide benzoxazole, poly-(diphenyl sulfide), polyester, aromatic polyamide, aromatic polyimide or polyetherimide, acrylic resin and poly-(vinyl alcohol).Can be used for the present invention as fluoropolymers such as tetrafluoroethylene.In addition,, well known to a person skilled in the art natural organic fiber in addition, cotton, burlap, felt, carbon fiber textiles are for example arranged and as natural cellulose textiless such as kraft paper and cotton paper and the paper that contains glass fibre as strengthening material.Described reinforcement filler can provide with the form of monfil or multifilament fiber, and can use separately or by weave altogether or examine/shell, side by side configuration, tangerine type (orange-type) or matrix and protofibril structure or fiber other known method of technician of making the field to use with the fiber combinations of other types.Described filler can be supplied with for example form of fiber strengthening fabric, non woven fibre strengthening material or paper.
Above-mentioned formed body preferably has according to the flame retardant resistance more than the V-2 of UL-94 stdn flame retardant resistance test.Can fully satisfy electronic material formed material, tackiness agent and the desired flame retardant resistance of coating according to the flame retardant resistance more than the V-2 of UL-94 stdn flame retardant resistance test.
The curable resin composition that comprises resin combination (resin combination (1)~(3) and other composition) of the present invention can be used as sealing material, as semiconductor sealing material.Hereinafter, will be described as the situation of sealing material using curable resin composition of the present invention.Following mineral filler, fire retardant, other additive etc. can be preferred for described curable resin composition, and if necessary can suitably be used for above-mentioned resin combination.
Curable resin composition of the present invention can contain to be useful on and improves water absorbability, suppresses coefficient of linear expansion, increases thermal conductivity and improve the mineral filler of mechanical properties.The example of mineral filler has: the powder of fused silica, crystalline silica, aluminum oxide, zircon, Calucium Silicate powder, lime carbonate, calcium titanate, silicon carbide, silicon nitride, aluminium nitride, boron nitride, beryllium oxide, zirconium white, zircon, forsterite, lardite, spinel, mullite and titanium dioxide etc.; The pearl that these material sphericalizations are obtained; And glass fibre.In addition, the example to the effective mineral filler of flame retardant resistance has aluminium hydroxide, magnesium hydroxide, zinc borate and zinc molybdate.These mineral fillers can be used separately, also can be with being used in combination in them.Among above-mentioned mineral filler, preferred molten silicon-dioxide with regard to suppressing coefficient of linear expansion, preferred aluminum oxide with regard to high thermal conductivity, the filler shape is preferably sphere with regard to flowability during with regard to moulding and the mould loss.With regard to formability, water absorbability, coefficient of linear expansion reduction and improved strength, curable resin composition of the present invention with respect to 100 weight parts, the add-on of mineral filler is preferably more than or equals 70 weight parts, 100 weight parts~1000 weight parts more preferably, and then more preferably 200 weight parts~950 weight parts.If it is less than 70 weight parts, then anti-backflow sexual orientation is in reduction, if it surpasses 950 weight parts, then flowability is tended to deficiency.
As fire retardant, known halogen based flame retardant of routine and the combination of no antimony based flame retardant can be used for curable resin composition of the present invention.The example of fire retardant has: nitrogenous compound, and phosphorous/nitrogen compound as cyanuric acid derivative and tricarbimide derivative, as ring phosphine nitrile, and metallic compound, as zinc oxide, ferric oxide, molybdenum oxide and ferrocene.
With regard to improve as the wet fastness and high temperature placement character of semiconductor devices such as IC with regard to, can add anionite.Described anionite is not subjected to concrete restriction, can use common known anionite.Example has hydrotalcite and is selected from the hydrous oxide of the element in magnesium, aluminium, titanium, zirconium and the bismuth, and these compounds can use separately, also can be with being used in combination in them.Especially, the hydrotalcite that limits by following general formula:
Mg
1-TAlt(OH)
2(CO
3)
t/2·m’H
2O
In this formula, 0<T≤0.5; And m ' is a positive integer.
If necessary, curable resin composition of the present invention can further contain following compound as other additive: releasing agent, as higher fatty acid, higher fatty acid metal-salt, ester wax, polyolefins wax, polyethylene and polyoxyethylene; Tinting material is as carbon black; With the stress conditioning agent, as silicone oil and silicone rubber powder.
As in the situation of sealing agent, can prepare curable resin composition of the present invention by any way, but need only this mode homodisperse and mix various raw materials; But,, can adopt following method: with the raw material of mixing tank thorough mixing predetermined amount, with mixing roll or forcing machine raw materials melt is mediated afterwards, more successively with raw material cooling and pulverizing as usual way.Have the appropriate size that is used for condition of molding and the flap of weight if raw material made, then make to handle to become easy.
Utilizing the example of the electronic part apparatus that curable resin composition of the present invention obtains by sealing equipment can be the electronic part apparatus that obtains by following manner: will be such as active component (semi-conductor chip for example, transistor, diode and thyristor etc.) and passive element (electrical condenser for example, resistance and coil) etc. element be installed in holding components (lead frame for example, the tape carrier that has connected up (already-wired tap carrier), running board, glass and silicon wafer) on, and seal necessary parts with encapsulating epoxy resin formed material of the present invention.The example of electronic part apparatus can comprise general resin package type IC, DIP (Dual Inline Package) for example, PLCC (PlasticLeaded Chip Carrier), QFP (Quad Flat Package), SOP (Small OutlinePackage), SOJ (Small Outline J-lead package), TSOP (Thin Small OutlinePackage) and TQFP (Thin Quad Flat Package), described example obtains by following manner: semiconductor device is fixed on the lead frame, by lead-in wire bonding and bump contact (bump) will such as welded disc sub-terminal parts such as (boning pad) be connected with leading part, use curable resin composition of the present invention the element that is obtained to be sealed then by transfer molding.Can also mention the TCP (Tape Carrier Package) that the semi-conductor chip sealing that is connected to tape carrier through bump contact is obtained by with curable resin composition of the present invention.In addition, the example comprises: by seal with curable resin composition of the present invention such as active component such as semi-conductor chip, transistor, diode and thyristor and/or such as passive elements such as electrical condenser, resistance and coil (these elements by lead-in wire bonding, flip chip bonding or welding is connected in running board and in the wiring of formation on glass) electronic part apparatus that obtains, as COB (Chip On Board) module, mixing IC and multi-chip module; With obtain by following manner as BGA (Ball Grid Array) and CSP electronic part apparatus such as (Chip Size Package): have in being installed on element overleaf on the front of organic substrate of running board terminal for connecting, by bump contact or lead-in wire bonding described element is connected with wiring on being formed at described organic substrate, seals described element with curable resin composition of the present invention afterwards.
The method of using curable resin composition sealing element of the present invention is low pressure transfer molding method the most normally; Yet, also can use injection moulding and compressed moulding method.
Electricly can obtain by following manner with circuit board: if necessary, with solvent cut curable resin composition of the present invention; Mix above-mentioned curing catalyst, filler and fire retardant etc. to obtain the running board insulating material; Flood various strengthening materials or described insulating material is coated various substrates with described insulating material; Dry also removing desolvated; And solidify described insulating material.The electric example with circuit board of gained can comprise single or double or MULTILAYER COMPOSITE type laminated plates, glass-epoxy type laminated plates, aromatic polyamide-epoxy type laminated plates, metal matrix circuit board and stack-up type circuit board.
Above-mentioned solvent is preferably those and has at least a solvent that comprises the structure of above-mentioned ehter bond, ester bond and nitrogen-atoms, make optimized viscosity with painting process or according to drying conditions in order to flood, solvent can use separately, also two or more solvents can be used with the form of mixture.Can use identical filler and the fire retardant used with above-mentioned semiconductor sealing material.
As strengthening material, can use material, the especially preferred glass fibers of above-mentioned institute example and weaving cotton cloth and non-woven fabrics of aromatic polyamide fibre, described material can use separately, also can be with being used in combination in them.
Curable resin composition of the present invention also can be preferred for: the raw material of producing Resins, epoxy; Molding material such as material of construction, valve jacket, laminated plates, stack-up type circuit board, solder resist, sealing material (being actually sealing material for semiconductor), injection material, mechanical part, electronics and moulding products such as electric component, vehicle, boats and ships and aircraft; With such as raw materials for production such as tackiness agent and electric insulation coating.
To be described as the maleimide compound of organic resin contained in the resin combination of the present invention (3) being suitable for.As maleimide compound, can use the compound that in a molecule, has all kinds of two above maleimide base groups.Single maleimide compound has high toxicity, thereby does not preferably use in the present invention.
The preference of above-mentioned maleimide compound comprises: cocondensation product bismaleimides, N for example, N '-ethylenebis maleimide, N, N '-hexa-methylene bismaleimides, N, a N '-penylene bismaleimides, N, N '-to the penylene bismaleimides, 2,2-two [4-(4-maleimide phenoxy group) phenyl] propane, two [4-(4-maleimide phenoxy group) phenyl] methane, 1,1,1,3,3,3-hexafluoro-2,2-two [4-(4-maleimide phenoxy group) phenyl] propane, N, N '-p, p '-phenylbenzene dimetylsilyl bismaleimides, N, N '-4,4 '-diphenyl ether bismaleimides, N, N '-methylene radical two (3-chlorine is to phenylene) bismaleimides, N, N '-4,4 '-sulfobenzide bismaleimides, N, N '-4,4 '-dicyclohexyl methyl hydride bismaleimides, N, N '-Dimethylenecyclohexacompound bismaleimides, N, N '-m-xylene bismaleimides, N, N '-4,4 '-phenylbenzene hexanaphthene bismaleimides; With N-phenylmaleimide with such as the cocondensation compound of aldehyde compounds such as acetaldehyde, phenyl aldehyde and hydroxy phenyl formaldehyde.In addition, preference can comprise the bismaleimide compound that is limited by following general formula:
In this formula, R
38The expression divalent group
Q
1Be the group that is directly connected in two aromatic nucleus, expression is selected from least a group in the group of being made up of the bivalent hydrocarbon radical with 1~10 carbon atom, hexafluoroisopropyli,ene, carbonyl, sulfenyl, sulfinyl, alkylsulfonyl and oxygen base.In fact, preference has 1,3-two (3-maleimide phenoxy group) benzene, two [4-(3-maleimide phenoxy group) phenyl] methane, 1,1-two [4-(3-maleimide phenoxy group) phenyl] ethane, 1,2-[4-(3-maleimide phenoxy group) phenyl] ethane, 2,2-two [4-(3-maleimide phenoxy group) phenyl] propane, 2,2-two [4-(3-maleimide phenoxy group) phenyl] butane, 2,2-two [4-(3-maleimide phenoxy group) phenyl]-1,1,1,3,3, the 3-HFC-236fa, 4, two (the 3-maleimide phenoxy group) biphenyl of 4-, two [4-(3-maleimide phenoxy group) phenyl] ketone, two [4-(3-maleimide phenoxy group) phenyl] thioether, two [4-(3-maleimide phenoxy group) phenyl] sulfoxide, two [4-(3-maleimide phenoxy group) phenyl] sulfone, two [4-(3-maleimide phenoxy group) phenyl] ethers and the compound that limits by following general formula:
In this formula, Q
2Expression can have substituent divalent group with aromatic nucleus; N represents the repeat number of average out to 0~10).Q
2Example be preferably the divalent group (phenylene, biphenylene and naphthylidene etc.) of phenyl, xenyl and naphthyl etc.
Usually when adding linking agent (as polyamine and aromatic amine compound) known and commonly used, use above-mentioned maleimide compound, the electron density e value unsaturated compound different with the unsaturated link(age) of maleimide can form charge-transfer complex and crosslinking structure improves thermotolerance thereby especially add, thereby described interpolation is preferred.
The compound that forms charge-transfer complex with above-mentioned maleimide compound is preferably: with 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihydroquinoline, poly-(2,2,4-trimethylammonium-1, the 2-dihydroquinoline), vinylbenzene, alpha-methyl styrene, anti--toluylene, vinyl ferrocene, 4-vinylpridine, 2-pseudoallyl naphthalene, N-vinylcarbazole, N-vinyl indoles, indoles, cumarone, furans, dihydrofuran, 3,4-dihydro-2-pyrans and 4H-chromene are the cyclic vinyl ether of representative; With acetate furfuryl group ester is the furan derivatives of representative; With Octadecane base vinyl ether and ethyl vinyl ether is the alkyl vinyl ether of representative; With ketene diacetal, acetate pseudoallyl ester and 1-amino-1-methoxy-ethylene are the ketone of representative, ester, lactone, aldehyde, acid amides, the enol ether of the carbonyl compound of lactan etc., enol ester, allyl acetate, vinyl-acetic ester, 1,2-dimethoxy ethene Dui dioxine, 2-chloroethyl vinyl ether, 2-phenyl vinyl alkyl oxide, 2-phenyl alkene ether, seven fluorine sec.-propyl alkene ethers, the ethyl vinyl thioether, styryl thiazolinyl thioether Dui Evil diene (p-oxadiene), cyclopentenes, tetrahydrobenzene, divinyl ether, divinyl, isoprene, 1, the 3-pentadiene, 1,4-pentadiene and dimethyl divinyl silane.
Above-mentioned resin combination (3) is to comprise the compound compositions with dimaleoyl imino.Resin combination (3) is not specifically limited, as long as it contains the maleimide compound as organic resin; Yet described composition preferably combination contains other organic resin composition, and this is because thermotolerance is further improved, keep simultaneously other organic resin characteristic.The described organic resin that can be used in combination is preferably above-mentioned compound and above-mentioned polyphenolic substance with at least one glycidyl and/or epoxy group(ing).In being used in combination the situation of these preferred organic resins, can similarly use above-mentioned additive, as solidifying agent.
For the content of described organic resin in above-mentioned resin combination (3), with the gross weight of organic resin and silane compound (if used solidifying agent, then for the gross weight of organic resin, silane compound and solidifying agent) be set under the situation of 100 weight %, lower value is preferably 20 weight %, more preferably 30 weight %.Higher limit is preferably 97 weight %, more preferably 90 weight %, and then more preferably 80 weight %.
For the content of above-mentioned silane compound in above-mentioned resin combination (3), with the gross weight of organic resin and silane compound (if used solidifying agent, then for the gross weight of organic resin, silane compound and solidifying agent) be set under the situation of 100 weight %, lower value is preferably 3 weight %, more preferably 10 weight %, and then more preferably 15 weight %.Higher limit is preferably 80 weight %, more preferably 70 weight %, and then more preferably 60 weight %.
With respect to 100 weight % of organic resin, the content of maleimide compound is preferably 2 weight %~100 weight % in the above-mentioned organic resin, more preferably 5 weight %~100 weight %.
Above-mentioned resin combination (3) (being also referred to as curable resin composition (3)) can be preferably be used for the purposes identical with (2) with above-mentioned resin combination (1) as the material of processibility and excellent heat resistance.
Preferably above-mentioned resin combination is the thermosetting adhesive resin combination that comprises thermosetting resin and above-mentioned silane compound.Above-mentioned silane compound mainly comprises by the organic backbone that makes at least one have the imide key and is connected in the structural unit that the Siliciumatom that forms siloxane bond forms.In view of the above, described resin combination can show more excellent characteristic, as thermotolerance, weathering resistance, formability, resistance to pressure and machinery and chemical stability.In addition, even described resin combination is applied bigger shearing force or make described resin combination moulding in the high temperature and high pressure environment, the bonded permanent magnet that comprises described thermosetting adhesive resin combination and magnet powder (mainly containing rare earth alloy) can generate the bonded permanent magnet that reduces hardly as physical propertiess such as magnetic propertiess with compositions of thermosetting resin.For example, in common bonded permanent magnet,,, thereby reduce Coercive Force in the magnetic properties meeting deterioration of powder described in thermoforming operations such as injection molding and extrusion moulding if thereby ferromagnetic metal powder, especially rare-earth magnet powder and resin glue are mediated the production bonded permanent magnet.But, the described thermosetting adhesive resin combination that comprises thermosetting resin and silane compound can fully suppress magnetic properties because thermo-contact in molding procedure and deterioration.Thereby, can produce the bonded permanent magnet that shows excellent magnetic property etc.In addition, described bonded permanent magnet can be produced the bonded permanent magnet that can be preferred for as various products such as electrical equipment, signal equipment and audio-frequency apparatus, medical equipment, general industry equipment and electronic vehicle devices with compositions of thermosetting resin.That is, mainly comprise the organic resin composition that contains above-mentioned thermosetting resin, the thermosetting adhesive resin combination that can be used as bonded permanent magnet formation usefulness magnetic powder tackiness agent, wherein said thermosetting adhesive resin contains above-mentioned silane compound.In addition, preferred implementation of the present invention comprises that also bonded permanent magnet wherein comprises the embodiment of above-mentioned thermosetting adhesive resin combination and magnetic powder (mainly comprising rare earth alloy) with compositions of thermosetting resin.
Above-mentioned thermosetting adhesive resin combination mainly comprises organic resin composition and the above-mentioned silane compound that contains thermosetting resin.Described thermosetting adhesive resin combination has excellent thermotolerance.If described composition as the magnetic powder tackiness agent that forms bonded permanent magnet, then can be obtained to have the bonded permanent magnet of excellent Coercive Force and the magnetic properties that do not reduce magnetic powder.In conventional tackiness agent, if ferromagnetic metal powder (being specially the rare-earth magnet powder) and resin glue are mediated, and mixture carried out as thermoforming steps such as injection molding and extrusion mouldings, then the magnetic properties deterioration of magnetic powder and Coercive Force reduce.But, use thermosetting adhesive resin combination of the present invention can produce the not bonded permanent magnet of deterioration of described characteristic.
Above-mentioned thermosetting adhesive resin combination mainly contains the organic resin composition that comprises thermosetting resin.The example of described thermosetting resin comprises having compound at least a in glycidyl and the epoxy group(ing), polyphenolic substance and maleimide compound.These compounds can use separately, also can be used in combination of two or more.Thereby preferred implementation of the present invention comprises: wherein above-mentioned organic composition comprises have compound at least a in glycidyl and the epoxy group(ing) embodiment of (being also referred to as organic resin composition (1)); Wherein above-mentioned organic resin composition comprises the embodiment of polyphenolic substance (being also referred to as organic resin composition (2)); Wherein the organic resin composition comprises the embodiment of maleimide compound (being also referred to as organic resin composition (3)).
Except above-mentioned organic resin, thermosetting resin for example melamine resin, guanamine resin, urea resin, xylene resin, urethane resin, Synolac, unsaturated polyester resin, epoxy (methyl) acrylate resin, vinyl ether resin, bismaleimides-cyanate resin and polyaniline resin also is excellent.
The content of above-mentioned silane compound is not subjected to concrete restriction in the described thermosetting adhesive resin combination, as long as contain described silane compound in the described thermosetting adhesive resin.Preferably the content of silane compound is 3 weight %~80 weight % with respect to the total solids level of thermosetting adhesive resin combination.If the content of silane compound, then may not fully show the above-mentioned effect that the silane compound that added causes less than 3 weight %, as stable on heating improvement.If the content of silane compound is greater than 80 weight %, then silane compound mixes inhomogeneously with resinous principle, thereby may not fully show described performance.The content of described silane compound is 5 weight %~70 weight % more preferably, and then more preferably 10 weight %~60 weight %.That is, be limited to 5 weight % down, be preferably 10 weight % especially.The upper limit is preferably 70 weight %, is preferably 60 weight % especially.The total solids level of thermosetting adhesive resinous principle is meant the gross weight of organic resin composition and silane compound.
Be used for bonded permanent magnet if will comprise the thermosetting adhesive resin combination of above-mentioned silane compound, then can improve the heat durability of the composition (bonded permanent magnet compositions of thermosetting resin) that comprises the magnetic powder that mainly contains rare earth alloy (the insoluble powder of forming by rare earth alloy).The heat durability of above-mentioned alloy magnetic powder is because described silane compound is deposited on the magnetic-particle surface because of the reason of mixing improved work of described silane compound and effect.Promptly, if contained silane compound is deposited on the magnetic-particle surface in the thermosetting adhesive resin combination, then bonded permanent magnet can improve with the heat-resisting degradation property of compositions of thermosetting resin, even and described composition be in for a long time that magnetic properties can deterioration yet in the hot environment.Thereby described bonded permanent magnet can be preferred for various application with compositions of thermosetting resin.That is, preferred implementation of the present invention comprises that wherein resin combination is the embodiment of bonded permanent magnet with resin combination.Thereby described heat durability is meant upper layer oxidized character that magnetic properties is descended under hot environment of magnetic powder.Can assess described heat durability according to the increase of the weight of resin combination under hot environment.And described oxidation may cause the deterioration of the mechanical characteristics of bonded permanent magnet.If above-mentioned resin combination is used to produce bonded permanent magnet, preferably above-mentioned silane compound has the silica chain (Si-O-Si) and have a structure that carbon containing organic composition wherein is connected with the silica chain in main chain.That is, preferably above-mentioned silane compound is the polysiloxane that contains the organic group with imide group.If above-mentioned silane compound is a polysiloxane, then thermotolerance, resistance to pressure, machinery and chemical stability and thermal conductivity are excellent more, and can provide excellent various characteristics such as thermotolerance for various materials.For example, if thereby silane compound shows high-dissolvability to various polymkeric substance as described in suitably selecting to make as siloxane backbone and the structures such as organic backbone that contain the imide key, then can easily give described polymkeric substance with thermotolerance and resistance to pressure etc.Can form the curing article that various characteristics also reduces hardly under as severe condition such as high temperature and high pressures even be endowed the polymkeric substance of thermotolerance and resistance to pressure etc.Thereby described polymkeric substance can be preferred for bonded permanent magnet application etc.
If above-mentioned resin combination as the bonded permanent magnet compositions of thermosetting resin, then in the application that needs heat durability strongly, is preferably used the silane compounds that demonstrate the effect that deposits to the magnetic powder surface more.In described application, wherein to comprise the embodiment of silane compound be preferred because above-mentioned deposition effect is excellent to resin combination, but the degree of described effect depends on the molecular structure of silane compound etc.
Except above-mentioned effect, described resin combination also can show stripping result, and this is because described resin combination comprises silane compound.Particularly, if described resin combination comprises thermosetting resin (particularly being epoxy material) as the organic resin composition, then because described organic resin composition has bonding effect, so described thermosetting adhesive resin combination may be attached on the mould when described composition is cured.The resin combination that contains an amount of described silane compound can show stripping result, thereby the curing article demoulding easily of described resin combination.Therefore, described resin combination is preferred for producing bonded permanent magnet.
Preferred implementation of the present invention comprises: comprise above-mentioned thermosetting adhesive resin combination and mainly contain the bonded permanent magnet compositions of thermosetting resin of the magnetic powder of rare earth alloy.Thereby, if described resin combination mainly comprises thermosetting adhesive resin combination and rare earth alloy, then can improve thermotolerance and heat durability and not reduce the powder magnetic properties.Thereby, can produce bonded permanent magnet with excellent Coercive Force.Bonded permanent magnet of the present invention has the effect of described excellence with compositions of thermosetting resin, thereby can produce the bonded permanent magnet that can be preferred for such as various products such as electrical equipment, signal equipment and audio-frequency apparatus, medical equipment, general industry equipment and car electronics.As mentioned above, contained silane compound is deposited on the surface of the magnetic powder that mainly contains rare earth alloy in the thermosetting adhesive resin combination, thereby shows heat durability.
Therefore, preferred implementation of the present invention is included in the bonded permanent magnet that contains silane compound in the above-mentioned thermosetting adhesive resin combination with compositions of thermosetting resin or comprise the bonded permanent magnet compositions of thermosetting resin of above-mentioned thermosetting adhesive resin combination (thermosetting adhesive resin combination) and rare earth alloy powder.
The above-mentioned magnetic powder that mainly comprises rare earth alloy is not specifically limited, as long as it contains rare earth alloy and shows magnetic.That is, preferably it comprises as at least a element in iron, cobalt, nickel and the manganese with element of magnetic.That is the powder that, comprises the alloy of at least a element in iron or cobalt, nickel and the manganese and rare earth element.The powder that more preferably comprises the alloy of iron or cobalt.Preferably will be such as various magnetic powders such as rare earth element-iron-boron powder, rare earth element-iron-nitrogen powder and rare earth element-cobalt dusts as described magnetic rare earth alloy.Among these, preferred rare earth element-iron-nitrogen magnetic powder.Among Sm, Nd, Pr, Y, La, Ce, Gd, Dy and the Tb one or more can be preferably used as above-mentioned rare earth element.If used two or more among them, they can have been used as mixture.Among these, preferred Sm and Nd.
The above-mentioned magnetic powder that mainly contains rare earth element and iron can also contain other compositions except rare earth element and iron.Described other composition is not subjected to concrete restriction, as long as described magnetic powder shows magnetic.For example, preferred usually as the various magnetic powders of bonded permanent magnet, as ferrite and alnico with raw material.For as the above-mentioned various magnetic powders of bonded permanent magnet, can preferably use anisotropic magnetic powder and isotropy magnetic powder with raw material.These magnetic powders preferably use by mixing with the above-mentioned magnetic powder that mainly comprises rare earth element and iron.
Above-mentioned other composition particularly, as the various magnetic powders of bonded permanent magnet with raw material, has the anisotropy field (HA) more than or equal to 50kOe.
Preferably above-mentioned magnetic powder contains 5at.% (atom the %)~Sm of 40at.% or Fe or the Co of Nd and 50at.%~90at.%.
Preferably above-mentioned magnetic powder has the median size that is less than or equal to 5 μ m.Preferred median size is specially and is less than or equal to 3 μ m.If median size is greater than 5 μ m, formability deterioration then, thereby described powder may not be preferably used as the bonded permanent magnet raw material.
For thermosetting adhesive resin combination in the above-mentioned bonded permanent magnet usefulness compositions of thermosetting resin and the ratio between the rare earth alloy, preferably, contain the thermosetting adhesive resin combination of 0.1 weight part~100 weight parts with respect to the rare earth alloy of 100 weight parts.If the thermosetting adhesive resin combination is less than 0.1 weight part, the physical strength of the curing article of described resin combination may be not enough.If it greater than 100 weight parts, then may not obtain required magnetic properties.More preferably, comprise the thermosetting adhesive resin combination of 1 weight part~50 weight parts, and then more preferably comprise the thermosetting adhesive resin combination of 3 weight parts~30 weight parts.
If desired, above-mentioned bonded permanent magnet can contain other compositions with resin combination, as is used for solidified composition (solidifying agent), as long as this bonded permanent magnet contains above-mentioned thermosetting adhesive resin combination and rare earth alloy powder with resin combination.Above-mentioned solidifying agent can be preferably used as above-mentioned solidifying agent.Particularly, the preferred thermosetting resin such as compound, polyphenolic substance and maleimide compound that contains epoxy group(ing) and/or glycidyl as described thermosetting adhesive resin combination.Can use and be used to reagent that solidifies described compound etc.
Above-mentioned other compositions can contain the additive except that above-mentioned solidifying agent.The example comprises stablizer, releasing agent, coupling agent, tinting material, softening agent, thinner (as solvent and reaction diluent), softening agents, various rubber material, sensitizer, filler, fire retardant and pigment.
, various compositions contained in the composition are carried out the blended method be not subjected to concrete restriction with in the compositions of thermosetting resin at above-mentioned bonded permanent magnet.Can use such as mixing machines such as ribbon blender, cylinder, Nautamixer, Henschel mixer, super mixing tank and planetary-type mixers, and such as kneaders such as Banbury mixer, kneader, roll, rough kneader (kneader Ruder), single screw extrusion machine and twin screw extruders.
Preferably be used to mix above-mentioned bonded permanent magnet with the mixing machine of compositions of thermosetting resin can prevent described compositions of thermosetting resin when mixing since the heat release that rubs solidify.Particularly, preferably described mixing machine has low-shearing power and has refrigerating function.Described composition becomes the bulk form by mixing, thus preferably by following forming method with described composition molding to produce bonded permanent magnet.
Preferably make the curable resin composition moulding of above-mentioned bonded permanent magnet by injection, compressed moulding method, extrusion moulding, roll-forming method or transfer molding method.Thereby, can easily produce and have excellent rust-preventing characteristic, physical strength, flexibility, thermotolerance and magnetic properties and the bonded permanent magnet of shape handiness.
Effect of the present invention
Resin combination of the present invention and curing article thereof have above-mentioned structure, and the invention provides silane compound, its production method that can be used for resin combination and the resin combination that contains described silane compound, even described resin combination has excellent thermotolerance, resistance to pressure, machinery and chemical stability and thermal conductivity and can form the curing article that also reduce physical properties under as severe rugged environments such as high temperature and high pressures hardly.
Embodiment
Hereinafter describe the present invention with reference to embodiment, yet, the invention is not restricted to these embodiment.Unless otherwise noted, " part " expression " weight part ", " % " expression " weight % ".
Label symbol n in the following chemical formula represents the repetition of the siloxane bond in the bracket, and the chemical formula of the compound that obtains in each synthesis example shows the main composition of institute's synthetic compound.
Synthesis example 1
Synthesizing of poly-(γ-phthalimide-based) propyl group silsesquioxane
86.6g in the four neck flasks of the 500mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the 3-TSL 8330 of the diglyme and the 179.4g of molecular sieve drying, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 100 ℃ with the water in the removal system.Next, make the temperature of reaction soln remain on 80 ℃, in 30 minutes, divide the Tetra hydro Phthalic anhydride that adds 148.2g for four times.After finishing, adding in 3 hours, confirms the Tetra hydro Phthalic anhydride completely consumed with high performance liquid chromatography.
To reaction product sampling and pass through
1H-NMR,
13C-NMR, MALDI-TOF-MS measure and find to contain in this product the compound that limits with following chemical formula (21).
1HNMR:0.72(t,2H),1.81(m,2H),3.48(dd,2H),3.72(s,9H),4.71(bs,1H),7.56-7.72(m,2H),7.73-7.86(m,2H),11.0(bs,1H)
13C-NMR:9.1,22.2,40.6,50.5,122.3,122.4,122.5,132.4,134.0,134.2,168.7,172.0
MALDI-TOF-MS:334(M+Li)
Next, the deionized water of disposable adding 54.2g, temperature is being raise so that by-product carbinol refluxes by total condenser and makes after reaction system keeps 6 hours, substitute total condenser with partial condenser, and elevated temperature once more, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 7.9g, and according to original state, elevated temperature reclaims water of condensation simultaneously once more, with 3 hours temperature is elevated to 160 ℃, make reaction soln remain on this temperature 2 hours and be cooled to room temperature.
Reaction product is the Vandyke brown high viscosity liquid that contains 80.6% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 2310, and weight-average molecular weight is 2830.Carry out
1H-NMR and
13C-NMR measures and finds to contain in the reaction product compound that limits with following chemical formula (22).
1HNMR:0.3-0.9(bs,2H),1.5-1.8(bs,2H),3.4-3.6(bs,2H),7.1-7.7(bs,4H)
13C-NMR:10.0,22.1,40.4,123.1,132.3,133.7,168.1
Synthesis example 2
Poly-(γ's-(1,8-naphthalimide) propyl group silsesquioxane) is synthetic
89.3g in the four neck flasks of the 300mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the N of molecular sieve drying, the 3-TSL 8330 of N '-N,N-DIMETHYLACETAMIDE and 29.7g, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 100 ℃ with the water in the removal system.Next, make it in statu quo remain on 100 ℃, in 30 minutes, divide four times and add 1 of 32.8g, 8-naphthalene dicarboxylic acids acid anhydride.After finishing, adding in 9 hours, confirms 1 with high performance liquid chromatography, the completely consumed of 8-naphthalene dicarboxylic acids acid anhydride.
To reaction product sampling and pass through
1H-NMR,
13C-NMR, MALDI-TOF-MS measure and find to contain in this product the compound that limits with following chemical formula (23).
1HNMR:0.61(t,2H),1.63(m,2H),3.26(dd,2H),3.45(s,9H),3.90(bs,1H),7.69(t,1H),7.79(t,1H),8.24-8.33(m,2H),8.38(d,1H),8.41(d,1H),11.0(bs,1H)
13C-NMR:7.0,21.7,42.8,49.2,123.8,127.5,127.8,127.9,130.7,130.9,131.1,131.9,134.7,135.0,163.5,170.3
MALDI-TOF-MS:384(M+Li)
Next, disposable adding is with the N of 6.2g, the 9.0g deionized water of N '-N,N-DIMETHYLACETAMIDE dilution, temperature is being raise so that by-product carbinol refluxes by total condenser and make reaction system after 95 ℃ keep 10 hours, substitute total condenser and elevated temperature once more with partial condenser, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 2.6g, and according to original state, elevated temperature once more, and when reclaiming water of condensation, with 3 hours temperature is elevated to 160 ℃ makes reaction soln remain on this temperature 2 hours and is cooled to room temperature.
Reaction product is the Vandyke brown high viscosity liquid that contains 37.1% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 1450, and weight-average molecular weight is 1500.Carry out
1H-NMR and
13C-NMR measures and finds to contain in the reaction product compound that limits with following chemical formula (24).
1HNMR:1.0-1.5(bs,2H),2.2-2.6(bs,2H),3.2-3.5(bs,2H),7.2-7.6(bs,2H),7.7-8.1(bs,2H),8.2-8.6(bs,2H)
13C-NMR:9.7,21.2,41.7,122.6,125.8,126.9,129.3,130.1,132.4,162.5
Synthesis example 3
Poly-(γ's-(5-norbornylene-2,3-imide) propyl group silsesquioxane) is synthetic
35.1g in the four neck flasks of the 300mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the 3-TSL 8330 of the diglyme and the 30.8g of molecular sieve drying, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 100 ℃ with the water in the removal system.Next, make it in statu quo remain on 100 ℃, in 30 minutes, divide the 5-norbornylene-2 that adds 28.2g for four times, the 3-dicarboxylic anhydride.After finishing, adding in 9 hours, confirms 5-norbornylene-2, the completely consumed of 3-dicarboxylic anhydride with high performance liquid chromatography.
To reaction product sampling and pass through
1H-NMR,
13C-NMR, MALDI-TOF-MS measure and find to contain in this product the compound that limits with following chemical formula (25).
1HNMR:0.40(t,2H),1.35(m,2H),1.46(dd,2H),3.08-3.17(m,1H),3.20(dd,2H),3.28-3.37(m,1H),3.40(s,9H),,3.42(m,1H),3.48(m,1H),5.91(s,2H),6.22(bs,1H),11.0(bs,1H)
13C-NMR:8.1,21.2,40.6,44.9,45.8,50.3,50.6,52.3,134.5,177.8,178.1
MALDI-TOF-MS:350(M+Li)
Next, the deionized water of disposable adding 9.3g, temperature is being raise so that by-product carbinol refluxes by total condenser and make reaction system after 95 ℃ keep 10 hours, substitute total condenser with partial condenser, and elevated temperature once more, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 1.4g, and according to original state, elevated temperature when reclaiming water of condensation, was elevated to 160 ℃ with 3 hours with temperature once more, make reaction soln remain on this temperature 2 hours and be cooled to room temperature.
Reaction product is the Vandyke brown high viscosity liquid that contains 58.2% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 2340, and weight-average molecular weight is 2570.Carry out
1H-NMR and
13C-NMR measures and finds to contain in the reaction product compound that limits with following chemical formula (26).
1HNMR:0.25-0.45(bs,2H),1.2-1.45(bs,2H),1.47(dd,2H),3.0-3.2(bs,4H),3.4-3.6(bs,2H),5.8-6.0(bs,2H)
13C-NMR:9.7,21.5,40.4,44.9,45.7,50.1,134.2,178.0
Synthesis example 4
Poly-(γ's-(six hydrogen-4-methyl phthalimide base) propyl group silsesquioxane) is synthetic
30.1g in the four neck flasks of the 300mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the 3-TSL 8330 of the dimethylbenzene and the 20.1g of molecular sieve drying, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 100 ℃ with the water in the removal system.Next, make it in statu quo remain on 100 ℃, in 30 minutes, divide the six hydrogen-4-methylphthalic acid acid anhydride that adds 18.8g for four times.After finishing, adding in 9 hours, confirms six hydrogen-4-methylphthalic acid acid anhydride completely consumed with high performance liquid chromatography.
To reaction product sampling and pass through
1H-NMR,
13C-NMR, MALDI-TOF-MS measure and find to contain in this product the compound that limits with following chemical formula (27).
1HNMR:0.72(t,2H),0.93(d,3H),1.21(m,2H),1.46(m,2H),1.60(m,2H),1.71(m,2H),1.81(m,1H),2.48(m,1H),2.63(m,1H),2.94(s,1H),3.22(m,2H),3.72(s,9H),6.6(s,1H)
13C-NMR:6.8,22.5,22.9,24.9,27.6,30.8,35.0,39.8,40.9,50.5,179.6,180.4
MALDI-TOF-MS:350(M+Li)
Next dilute the deionized water of 6.1g with the diglyme of 36.0g, disposable afterwards adding, temperature is being raise so that by-product carbinol refluxes by total condenser and make reaction system after 95 ℃ keep 10 hours, substitute total condenser with partial condenser, and elevated temperature once more, in the azeotrope that reclaims by-product carbinol and water of condensation and dimethylbenzene, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 1.4g, and according to original state, elevated temperature when reclaiming water of condensation and dimethylbenzene, was elevated to 160 ℃ with 3 hours with temperature once more, make reaction soln remain on this temperature 2 hours and be cooled to room temperature.
Reaction product is the Vandyke brown high viscosity liquid that contains 47.3% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 4080, and weight-average molecular weight is 4230.Carry out
1H-NMR and
13C-NMR measures and finds to contain in the reaction product compound that limits with following chemical formula (28).
1HNMR:0.45-0.70(bs,2H),0.88(d,3H),1.25-1.4(bs,2H),1.45-1.6(bs,2H),1.73(bd,2H),1.9-2.1(bs,1H),2.15-2.25(bs,1H),2.7-3.05(bs,2H),3.3-3.5(bs,2H)
13C-NMR:10.2,21.3,21.8,22.4,23.9,29.3,31.0,35.4,39.4,40.6,179.1
Synthesis example 5
Synthetic (2) of poly-(γ-phthalimide-based propyl group silsesquioxane)
37g in the four neck flasks of the 300mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the Tetra hydro Phthalic anhydride of the diglyme of molecular sieve drying, the 3-of 62.1g (triethoxysilyl) propyl group isocyanic ester and 37.2g, and when stirring, mixture heating up is refluxed beginning under with drying nitrogen round-robin condition, and, confirm the Tetra hydro Phthalic anhydride completely consumed with high performance liquid chromatography by keeping temperature to carry out the decarbonation reaction in 8 hours in stable back.
To reaction product sampling and pass through
1H-NMR,
13C-NMR, MALDI-TOF-MS measure, and find to contain in this product the compound that the chemical formula (21) in the synthesis example 1 limits, and wherein all are positioned at terminal methoxyl group and all replace to oxyethyl group.
Next the deionized water of disposable adding 13.6g, temperature is being raise so that by-product carbinol refluxes by total condenser and makes after reaction system keeps 6 hours, substitute total condenser with partial condenser, and elevated temperature once more, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 8.5g, and according to original state, elevated temperature when reclaiming water of condensation, was elevated to 160 ℃ with 3 hours with temperature once more, make reaction soln remain on this temperature 2 hours and be cooled to room temperature.
Reaction product is the Vandyke brown high viscosity liquid that contains 75.6% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 2280, and weight-average molecular weight is 2920.Carry out
1H-NMR and
13C-NMR measure to find to contain in the reaction product with synthesis example 1 in the identical compound that composition formula limited of chemical formula (22).
Synthesis example 6
Synthetic (3) of poly-(γ-phthalimide-based propyl group silsesquioxane)
20.2g in the four neck flasks of the 300mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the N of molecular sieve drying, the same exsiccant diglyme of N '-N,N-DIMETHYLACETAMIDE, 20.2g, the 3-r-chloropropyl trimethoxyl silane of 54.5g and the phthalic imidine of 40.3g, and under with drying nitrogen round-robin condition with mixture in 60 ℃ of stirrings, with the pyridine that dropwise added 26.1g in 4 hours.After dropwise adding is finished, continue to stir 8 hours, confirm the phthalic imidine completely consumed with high performance liquid chromatography at 80 ℃.
To reaction product sampling and pass through
1H-NMR,
13C-NMR, MALDI-TOF-MS measure and find to contain in this product the compound that the chemical formula (21) in the synthesis example 1 limits.
Next, the deionized water of disposable adding 14.8g, temperature is being raise so that by-product carbinol refluxes by total condenser and makes after reaction system keeps 6 hours, substitute total condenser with partial condenser, and elevated temperature once more, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 9.2g, and according to original state, elevated temperature when reclaiming water of condensation, was elevated to 160 ℃ with 3 hours with temperature once more, make reaction soln remain on this temperature 2 hours and be cooled to 60 ℃.
Reaction product is the Vandyke brown high viscosity liquid that contains 76.3% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 2330, and weight-average molecular weight is 3050.Carry out
1H-NMR and
13C-NMR measure to find to contain in the reaction product with synthesis example 1 in the identical compound that composition formula limited of chemical formula (22).
Synthesis example 7
Attempt from the synthetic of poly-(3-aminopropyl) silsesquioxane
In the four neck flasks of the 500mL that is equipped with agitator, temperature sensor and total condenser, pack into the 1N hydrochloric acid of 357.3g, and under the agitation condition of room temperature, add the 3-TSL 8330 of 42.7g and mixture was kept 3 hours, after being heated to 60 ℃, kept 4 hours then.Change the reaction soln that is obtained over to make square plate and in baking oven, place and spend the night removing volatile component, and then under the decompression of 120 ℃ and 5kPa, in baking oven, place 2 hours to obtain to gather (3-aminopropyl) silsesquioxane in 80 ℃ by PTFE.Output is 34.9g.
Because poly-(gamma-amino propyl group) silsesquioxane of reaction product is only water-soluble, so make 10% the aqueous solution, adds Tetra hydro Phthalic anhydride then, but can not obtain required reaction product, but generate a large amount of phthalic acids.
When the final silane compound that obtains is determined in to each synthesis example 1~7, pass through H
1-NMR spectrum does not detect alkoxyl group, and has confirmed silanol group by near-infrared spectra.Therefore, can confirm that these silane compounds have the silanol group that is positioned at molecular end.
Synthesis example 8
Synthesizing of poly-((suitable-4-tetrahydrobenzene-1, the 2-imide) propyl group silsesquioxane)
103.7g in the four neck flasks of the 500mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the 3-TSL 8330 of the diglyme and the 177.6g of molecular sieve drying, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 100 ℃ with the water in the removal system.Next, make the temperature of reaction soln remain on 80 ℃, in 30 minutes, divide the suitable-4-tetrahydrobenzene-1 that adds 150.7g for four times, the 2-dicarboxylic anhydride.After finishing, adding in 3 hours, confirms suitable-4-tetrahydrobenzene-1, the completely consumed of 2-dicarboxylic anhydride with high performance liquid chromatography.
To reaction product sampling and pass through
1H-NMR,
13C-NMR, MALDI-TOF-MS measure and find to contain in this product the compound that limits with following chemical formula (29).
1HNMR:0.72(t,2H),1.81(m,2H),2.23(dd,4H),2.74(m,1H),2.91(dd,1H),3.48(dd,2H),3.72(s,9H),5.74(m,2H),11.0(bs,1H)
13C-NMR:9.1,22.2,25.5,26.8,40.6,42.3,43.1,44.7,131.7,168.8,172.7
MALDI-TOF-MS:338(M+Li)
Next, the deionized water of disposable adding 53.4g, temperature is being raise so that by-product carbinol refluxes by total condenser and makes after reaction system keeps 6 hours, substitute total condenser with partial condenser, and elevated temperature once more, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 7.9g, and according to original state, elevated temperature when reclaiming water of condensation, was elevated to 160 ℃ with 3 hours with temperature once more, make reaction soln remain on this temperature 2 hours and be cooled to room temperature.
Reaction product is the Vandyke brown high viscosity liquid that contains 74.3% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 2041, and weight-average molecular weight is 2838.Carry out
1H-NMR and
13C-NMR measures and finds to contain in the reaction product compound that limits with following chemical formula (30).
1HNMR:0.25-0.55(bs,2H),1.3-1.5(bs,2H),2.0-2.5(dd,4H),2.9-3.1(bs,2H),3.2-3.35(bs,2H),5.65-5.8(bs,2H)
13C-NMR:10.0,21.0,23.8,39.0,41.1,127.8,180.5
The final product that obtains in synthesis example 1~4 and the synthesis example 8 is placed in the aluminium dish, and places so that the volatile component complete evaporation is isolated 5 kinds of silane compounds in the decompression baking oven with 5kPa in 160 ℃.Silane compound in synthesis example 1~4 and the synthesis example 8 corresponds respectively to silane compound A, B, C, D and E.
Silane compound A: poly-(γ-phthalimide-based propyl group silsesquioxane)
Silane compound B: poly-(γ-(1,8-naphthalimide) propyl group silsesquioxane)
Silane compound C: poly-(γ-(5-norbornylene-2,3-imide) propyl group silsesquioxane)
Silane compound D: poly-(γ-(six hydrogen-4-methyl phthalimide base) propyl group silsesquioxane)
Silane compound E: poly-((suitable-4-tetrahydrobenzene-2, the 3-imide) propyl group silsesquioxane)
<cagelike silsesquioxane 〉
Synthesis example 9
Synthesizing of eight (γ-phthalimide-based propyl group) silsesquioxane
According to reference 1 (F.J.Feher and K.D.Wyndham, Chem.Comm., 1998, the 323-324) synthetic technology described in has been synthesized eight (γ-phthalimide-based propyl group) silsesquioxanes and has been carried out following reaction.160.6g in the four neck flasks of the 300mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the diglyme of molecular sieve drying, eight (the 3-oronain propyl group) silsesquioxanes of 16.34g and the Tetra hydro Phthalic anhydride of 16.67g, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 60 ℃ with the water in the removal system, in 30 minutes, divide the diaza-bicyclo undecylene that adds 6.37g for four times.After adding is finished, make reaction soln confirm the Tetra hydro Phthalic anhydride completely consumed 60 ℃ of maintenances 4 hours and with high performance liquid chromatography.After being cooled to room temperature, reaction soln is filtered and isolating the faint yellow solid material.To reacting the filtrate sampling and passing through
1H-NMR,
13C-NMR, MALDI-TOF-MS measure and find to contain in this product the compound that limits with following chemical formula (31).
1HNMR:0.72(t,2H),1.81(m,2H),3.48(dd,2H),4.71(bs,1H),7.56-7.72(m,2H),7.73-7.86(m,2H),11.0(bs,1H)
13C-NMR:9.1,22.2,40.6,122.3,122.4,122.5,132.4,134.0,134.2,168.7,172.0
MALDI-TOF-MS:2073(M+Li)
And then, filtrate is turned back in the reaction unit once more and substituting total condenser with partial condenser, elevated temperature once more when reclaiming water of condensation, is elevated to 120 ℃ with 3 hours temperature with reaction soln afterwards.When temperature reaches 120 ℃, add the pyridine of 0.9g, and reclaim water of condensation simultaneously, with 3 hours temperature is elevated to 160 ℃, make reaction soln remain on this temperature 2 hours and be cooled to room temperature.
Reaction product is the Vandyke brown high viscosity solution that contains 25.3% involatile constituent, and by the GPC determining molecular weight time, observe very sharp-pointed peak: number-average molecular weight is 1915, and weight-average molecular weight is 1923.Carry out
1H-NMR and
13C-NMR measures and finds to contain in the reaction product compound that limits with following chemical formula (32).
1HNMR:0.41(t,2H),1.34(m,2H),3.27(t,2H),7.66(dd,2H),8.13(s,2H)
13C-NMR:9.2,21.0,40.7,123.1,132.3,133.7,168.1
MALDI-TOF-MS:1929(M+Li)
Synthesis example 10
Eight (γ's-(5-norbornylene-2,3-imide propyl group) silsesquioxane) is synthetic
According to reference 1 (F.J.Feher and K.D.Wyndham, Chem.Comm., 1998, the 323-324) synthetic technology described in has been synthesized eight (γ-oronain propyl group) silsesquioxanes and has been carried out following reaction.157.9g in the four neck flasks of the 300mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the diglyme of molecular sieve drying, eight (the 3-oronain propyl group) silsesquioxanes of 15.05g and the 5-norbornylene-2 of 17.02g, the 3-dicarboxylic anhydride, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 60 ℃ with the water in the removal system, in 30 minutes, divide the sodium tert-butoxide that adds 10.06g for four times.After adding is finished, make reaction soln confirm 5-norbornylene-2, the completely consumed of 3-dicarboxylic anhydride 60 ℃ of maintenances 4 hours and with high performance liquid chromatography.After being cooled to room temperature, reaction soln is filtered and isolating the faint yellow solid material.To filtrate sampling and pass through
1H-NMR,
13C-NMR, MALDI-TOF-MS measure and find to contain in this product the compound that limits with following chemical formula (33).
1HNMR:0.40(t,2H),1.35(m,2H),1.46(dd,2H),3.08-3.17(m,1H),3.20(dd,2H),3.28-3.37(m,1H),3.42(m,1H),3.48(m,1H),5.91(s,2H),6.22(bs,1H),11.0(bs,1H)
13C-NMR:8.1,21.2,40.6,44.9,45.8,50.6,52.3,134.5,177.8,178.1
MALDI-TOF-MS:2202(M+Li)
And then, filtrate is turned back in the reaction unit once more and substituting total condenser with partial condenser, elevated temperature once more when reclaiming water of condensation, is elevated to 120 ℃ with 3 hours temperature with reaction soln afterwards.When temperature reaches 120 ℃, add the pyridine of 0.9g, and when reclaiming water of condensation, temperature is elevated to 160 ℃ with 3 hours, make reaction soln remain on this temperature 2 hours and be cooled to room temperature.
Reaction product is the Vandyke brown high viscosity liquid that contains 25.1% involatile constituent, and by the GPC determining molecular weight time, observe very sharp-pointed peak: number-average molecular weight is 2020, and weight-average molecular weight is 2035.Carry out
1H-NMR,
13C-NMR and MALDI-TOF-MS measure and find to contain in the reaction product compound that limits with following chemical formula (34).
1HNMR:0.41(t,2H),1.34(m,2H),1.53(dd,2H),3.17(m,4H),3.27(t,2H),5.98(s,2H)
13C-NMR:9.2,21.1,40.7,45.0,46.0,52.3,134.6,177.8
MALDI-TOF-MS:2058(M+Li)
The final product liquid that obtains in synthesis example 9 and the synthesis example 10 is placed in the aluminium dish, and in 160 ℃ with 5kPa places in the decompression baking oven so that the volatile component complete evaporation, and isolate 4 kinds of silane compounds.Silane compound in the synthesis example 9 is silane compound F and H, and the silane compound in the synthesis example 10 is silane compound G and I.
Silane compound F: poly-(γ-phthalimide-based propyl group) silsesquioxane
Silane compound G: poly-(γ-(5-norbornylene-2,3-imide) propyl group) silsesquioxane
Silane compound H: eight (γ-(phthalimide-based propyl group) silsesquioxane)
Silane compound I: eight (γ-(5-norbornylene-2,3-imide) propyl group silsesquioxane)
Synthesis example 11
In the four neck flasks of the 500mL that is equipped with agitator, temperature sensor and total condenser, pack into the 1-dimethylsilane oxygen base-3,5,7,9,11,13 of the 67g (60mmol) that is dissolved in 600g toluene, 15-seven (trimethylsiloxy) five rings [9.5.1.1
3.9.1
5.15.1
7.13] eight siloxanes.Toluene solution (platinum of 3 weight %) to divinyl tetramethyl disiloxane platinum (0) complex compound that wherein adds 40mg.In room temperature under agitation, add the N of 13.7g (68mmol), two (trimethyl silyl) allyl amines of N-.Keeping stirring 24 hours afterreactions under room temperature finishes.Decompression concentrates reaction mixture down.With acetonitrile washing 3 times and the vacuum-drying of the crude product that obtained with 6mL.As a result, obtained the white solid of 68.6g.When by GPC the white solid that is obtained being measured, number-average molecular weight is 1348, and weight-average molecular weight is 1350.Carry out
1H-NMR,
13C-NMR and
13Si-NMR, MALDI-TOF-MS and GPC measure and find that the white solid that is obtained contains the compound that limits with following chemical formula (35):
Productive rate is 86.8%.Analytical results is as follows.
1HNMR:0.08(18H,s),0.13(6H,s),0.15(63H,s),0.50-0.44(2H,m),1.39-1.28(2H,m),2.85-1.67(2H,m)
13C-NMR:-0.5,1.2,1.3,2.1,14.9,28.6,49.0
13Si-NMR:-109.0,5.1,12.5
MALDI-TOF-MS:1338(M+Na+)
Next, in the four neck flasks of the 500mL that is equipped with agitator, temperature sensor and total condenser, pack into the compound, the Tetra hydro Phthalic anhydride of 3.3g and the diglyme of 100g that limit by following formula (35) of 27g.Under with the condition of nitrogen circulation, thereby the mixture stirring was removed volatile component by Rotary Evaporators in 8 hours.As a result, obtained the faint yellow solid of 29.3g.When measuring the faint yellow solid that is obtained with GPC, number-average molecular weight is 1340, and weight-average molecular weight is 1345.Also the faint yellow solid that is obtained has been carried out mass analysis mensuration by MALDI-TOF-MS.Obtained following result.
MALDI-TOF-MS:1338(M+Na+)
This compound that surface obtained as a result is the compound by following formula (36) expression:
Synthesis example 12
Utilize eight (dimethyl hydroxyl) silsesquioxane (trade(brand)name: OctaSilane POSS SH1310, the product of Hybrid Plastics) to substitute 1-dimethylsilane oxygen base-3,5,7,9,11,13,15-seven (trimethylsiloxy) five rings [9.5.1.1
3.9.1
5.15.1
7.13] eight siloxanes have obtained pale yellow powder.When measuring the faint yellow solid that is obtained with GPC, number-average molecular weight is 2476, and weight-average molecular weight is 2488.Also the faint yellow solid that is obtained has been carried out mass analysis mensuration by MALDI-TOF-MS.Obtained following result.
MALDI-TOF-MS:(M+Na+)
This compound that surface obtained as a result is the compound by following formula (37) expression:
The final product that obtains in the synthesis example 11~12 is placed in the aluminium dish, and in 160 ℃ with 5kPa places in the decompression baking oven so that the volatile component complete evaporation, and isolate 2 kinds of silane compounds.Silane compound J makes in synthesis example 11, is limited by following formula (36).Silane compound K makes in synthesis example 12, is limited by following formula (37).
<binder composition 〉
Synthesis example 13
Poly-(γ's-(octenyl succinimido) propyl group silsesquioxane) is synthetic
36.9g in the four neck flasks of the 300mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the diglyme of molecular sieve drying, the dimethylbenzene of 36.9g and the 3-TSL 8330 of 50.74g, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 100 ℃ with the water in the removal system.Next, remain in 80 ℃, in 30 minutes, divide the octenyl succinic acid anhydride (isomer mixture) that adds 60.10g for four times in the temperature that makes reaction soln.After finishing, adding in 3 hours, confirms the octenyl succinic acid anhydride completely consumed with high performance liquid chromatography.
Reaction product is being taken a sample and passing through
1When H-NMR measures, be difficult to measure detailed spectrogram, but found to be positioned at the singlet that belongs to the methoxy methyl silylation at δ=3.48ppm place with big integrated value owing to the aliphatics skeleton is huge; Be positioned at the wide singlet that belongs to NH group and COOH group respectively at δ=4.71ppm and 11.0ppm place; With the diastereoisomeric quartet that belongs to ethylenic linkage that is positioned at δ=5.72ppm place.In addition, carrying out
13C-NMR has found to be positioned at the peak that belongs to the methoxy methyl silylation at δ=50.5ppm place when measuring; Be positioned at the peak that belongs to the isomer that comes from ethylenic linkage at δ=126.3ppm, 130.6ppm, 134.7ppm and 138ppm place; With the peak that belongs to carbonyl carbon that is positioned at δ=177.0ppm and 179.9ppm place.In addition, measured MALDI-TOF-MS, the mass value of main peak is M=397 (M+Li), therefore can determine that product contains the compound that is limited by following chemical formula (38).
Next, the deionized water of disposable adding 15.3g, temperature is being raise so that by-product carbinol refluxes by total condenser and makes after reaction system keeps 6 hours, substitute total condenser with partial condenser, and elevated temperature once more, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 2.3g, and according to original state, elevated temperature when reclaiming water of condensation and toluene, was elevated to 160 ℃ with 3 hours with temperature once more, make reaction soln remain on this temperature 2 hours and be cooled to room temperature.
Reaction product is the Vandyke brown high viscosity liquid that contains 70.6% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 2420, and weight-average molecular weight is 3140.Carrying out
1H-NMR measures and spectrogram and above-mentioned chemical formula (35) when comparing, is found to be positioned at δ=3.48ppm, the peak disappearance at 4.71ppm and 11.0ppm place.Carrying out
13When C-NMR measures, find that the peak occurring at δ=172.7ppm and 176.3ppm place has replaced the peak that is positioned at δ=177.0ppm and 179.9ppm place.Therefore, can determine that reaction product contains the compound that is limited by following chemical formula (39).
Synthesis example 14
Poly-(γ's-(dodecenyl succinic succinimido) propyl group silsesquioxane) is synthetic
42.0g in the four neck flasks of the 300mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the diglyme of molecular sieve drying, the dimethylbenzene of 42.0g and the 3-TSL 8330 of 48.58g, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 100 ℃ with the water in the removal system.Next, remain in 80 ℃, in 30 minutes, divide the dodecenyl succinic anhydride (isomer mixture) that adds 72.89g for four times in the temperature that makes reaction soln.After finishing, adding in 3 hours, confirms the dodecenyl succinic anhydride completely consumed with high performance liquid chromatography.
Reaction product is being taken a sample and passing through
1When H-NMR measures, be difficult to measure detailed spectrogram, but found to be positioned at the singlet that belongs to the methoxy methyl silylation at δ=3.48ppm place with big integrated value owing to the aliphatics skeleton is huge; Be positioned at the wide singlet that belongs to NH group and COOH group respectively at δ=4.71ppm and 11.0ppm place; With the diastereo-isomerism quartet that belongs to ethylenic linkage that is positioned at δ=5.72ppm place.In addition, carrying out
13When measuring, C-NMR finds to have the peak that belongs to the methoxy methyl silylation that is positioned at δ=50.5ppm place; Be positioned at the peak that belongs to the isomer that comes from ethylenic linkage at δ=126.3ppm, 130.6ppm, 134.7ppm and 138ppm place; With the peak that belongs to carbonyl carbon that is positioned at δ=177.0ppm and 179.9ppm place.In addition, measured MALDI-TOF-MS, the mass value of main peak is M=453 (M+Li), therefore can determine that product contains the compound that is limited by following chemical formula (40).
Next, the deionized water of disposable adding 14.7g, temperature is being raise so that by-product carbinol refluxes by total condenser and makes after reaction system keeps 6 hours, substitute total condenser with partial condenser, and elevated temperature once more, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 2.3g, and according to original state, elevated temperature when reclaiming water of condensation and toluene, was elevated to 160 ℃ with 3 hours with temperature once more, make reaction soln keep this temperature 2 hours and be cooled to room temperature.
Reaction product is the Vandyke brown high viscosity liquid that contains 69.8% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 2890, and weight-average molecular weight is 3730.Carrying out
1H-NMR measures and spectrogram and above-mentioned chemical formula (37) when comparing, is found to be positioned at δ=3.48ppm, the peak disappearance at 4.71ppm and 11.0ppm place.Carrying out
13When C-NMR measures, find that the peak occurring at δ=172.7ppm and 176.3ppm place has replaced the peak that is positioned at δ=177.0ppm and 179.9ppm place.Therefore, can determine that reaction product contains the compound that is limited by following chemical formula (41).
The final product that obtains in synthesis example 13 and the synthesis example 14 is placed in the aluminium dish, and in 160 ℃ with 5kPa places in the decompression baking oven so that the volatile component complete evaporation, and isolate 2 kinds of silane compounds.Silane compound L makes in synthesis example 13.Silane compound M makes in synthesis example 14.
Silane compound L: poly-(γ-(octenyl succinimido) propyl group) silsesquioxane
Silane compound M: poly-(γ-(dodecenyl succinic succinimido) propyl group) silsesquioxane
Embodiment 1~9 and comparative example 1
The thermotolerance assessment of<silane compound 〉
Above-mentioned silane compound A~E and J~M are carried out the TGA analysis.For relatively, used polyphenylene silsesquioxane (trade(brand)name: PPSQ-H, industrial society produces by little westernization).
The TGA analysis condition is as follows.
Used instrument: TGA 50H (making) by Shimadzu Seisakusho Ltd.
Test condition: 30 ℃~550 ℃ of temperature ranges, 10 ℃/min of rate of heating, recycle gas: dry air 50mL/min., sampling weight 10mg~15mg.
By with above-mentioned silane compound 25 ℃ be immersed in 30% 1 week of aqueous sodium hydroxide solution test hydrolytic resistance.If this immersion outward appearance does not afterwards change then silane compound is chosen as well.Change or compound thoroughly decomposes and is dissolved in solution if can be observed, it is poor then silane compound to be chosen as.
Table 1
Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example 1 | |
Silane compound | ?A | ?B | ?C | ??D | ??E | ??J | ??K | ??L | ??M | ??PPSQ-H |
TGA 5% weight reduces temperature | ?463℃ | ?473℃ | ?441℃ | ??430℃ | ??465℃ | ??394℃ | ??380℃ | ??350℃ | ??338℃ | ??383℃ |
Hydrolytic resistance | Well | Well | Well | Well | Well | Difference | Difference | Difference | Well | Well |
As shown in table 1,5% weight of the silane compound under air cycle in the scope of the invention reduces temperature all more than or equal to 400 ℃, and the polyphenylene silsesquioxane of comparative example does not then reach 400 ℃.Among the application's silane compound, in the silane compound that comprises the imide group that contains the alkene chain (as compound L and M), heat decomposition temperature descends.This result shows, any aromatic nucleus as among silane compound A~E, heterocycle and alicyclic ring skeleton preferably as described in the imide skeleton.In addition, among the application's silane compound, with regard to improving thermotolerance and hydrolytic resistance, only has RSiO
3Structure as the silane compound A~E of main framing be better than have comprise a plurality of such as SiO
4And R
3The silane compound J and the K of the siloxanes main framing of silicon such as SiO bunch.
<to the assessment of the characteristic of the ratio that depends on the organic group that is connected with the Si atom〉with imide skeleton
Synthesis example 15
44.0g in the four neck flasks of the 200mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the diglyme of molecular sieve drying, the 3-TSL 8330 of 41.5g, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 100 ℃ with the water in the removal system.Next, remain in 80 ℃, in 30 minutes, divide the 5-norbornylene-2 that adds 38.0g for four times, the 3-dicarboxylic anhydride at reaction soln.After finishing, adding in 3 hours, confirms 5-norbornylene-2, the completely consumed of 3-dicarboxylic anhydride with high performance liquid chromatography.
Next, the deionized water of disposable adding 17.9g, temperature is being raise so that by-product carbinol refluxes by total condenser and makes after reaction system keeps refluxing 6 hours, substitute total condenser with partial condenser, and elevated temperature once more, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 1.3g, and according to original state, elevated temperature when reclaiming water of condensation, was elevated to 160 ℃ with 3 hours with temperature once more, make reaction soln remain on this temperature 2 hours and be cooled to room temperature.As a result, obtained silane compound N.
Silane compound N is the Vandyke brown high viscosity liquid that contains 62.1% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 2530, and weight-average molecular weight is 3010.Carrying out
1When H-NMR measured, the organic group of finding to contain the imide skeleton was 69.7% with respect to the ratio of the organic group that is connected with the Si atom.This ratio almost is equivalent to comprise the ratio of the charged organic group of imide skeleton.
Synthesis example 16
46.1g in the four neck flasks of the 200mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the diglyme of molecular sieve drying, the 3-TSL 8330 of 29.4g and the phenyltrimethoxysila,e of 32.5g, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 100 ℃ with the water in the removal system.Next, remain in 80 ℃, in 30 minutes, divide the 5-norbornylene-2 that adds 26.9g for four times, the 3-dicarboxylic anhydride at reaction soln.After finishing, adding in 3 hours, confirms 5-norbornylene-2, the completely consumed of 3-dicarboxylic anhydride with high performance liquid chromatography.
Next, the deionized water of disposable adding 17.7g, temperature is being raise so that by-product carbinol refluxes by total condenser and makes after reaction system keeps refluxing 6 hours, substitute total condenser with partial condenser, and elevated temperature once more, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 1.3g, and according to original state, elevated temperature when reclaiming water of condensation, was elevated to 160 ℃ with 3 hours with temperature once more, make reaction soln remain on this temperature 2 hours and be cooled to room temperature.As a result, obtained silane compound P.
Silane compound P is the Vandyke brown high viscosity liquid that contains 60.3% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 3300, and weight-average molecular weight is 3850.Carrying out
1When H-NMR measured, the organic group of finding to contain the imide skeleton was 50.3% with respect to the ratio of the organic group that is connected with the Si atom.This ratio almost is equivalent to comprise the ratio of the charged organic group of imide skeleton.
Synthesis example 17
47.0g in the four neck flasks of the 200mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the diglyme of molecular sieve drying, the 3-TSL 8330 of 22.6g and the phenyltrimethoxysila,e of 58.3g, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 100 ℃ with the water in the removal system.Next, remain in 80 ℃, in 30 minutes, divide the 5-norbornylene-2 that adds 20.9g for four times, the 3-dicarboxylic anhydride at reaction soln.After finishing, adding in 3 hours, confirms 5-norbornylene-2, the completely consumed of 3-dicarboxylic anhydride with high performance liquid chromatography.
Next, the deionized water of disposable adding 22.7g, temperature is being raise so that by-product carbinol refluxes by total condenser and makes after reaction system keeps refluxing 6 hours, substitute total condenser with partial condenser, and elevated temperature once more, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 1.3g, and according to original state, elevated temperature when reclaiming water of condensation, was elevated to 160 ℃ with 3 hours with temperature once more, make reaction soln keep this temperature 2 hours and be cooled to room temperature.As a result, obtained silane compound Q.Silane compound Q is the Vandyke brown high viscosity liquid that contains 60.3% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 3480, and weight-average molecular weight is 4010.Carrying out
1H-NMR finds when measuring, and the organic group that contains the imide skeleton is 30.8% with respect to the ratio of the organic group that is connected with the Si atom.This ratio almost is equivalent to comprise the ratio of the charged organic group of imide skeleton.
Embodiment 10 and 11 and the reference example
As carrying out in embodiment 1~9 and the comparative example 1, silane compound is carried out the assessment of TGA analysis and hydrolytic resistance.Table 2 has shown assessment result.In table 2, in order more also to have shown the assessment result of silane compound C and the silane compound PPSQ-H in the comparative example 1 used among the embodiment 3.Ratio in the table 2 has shown the organic group that contains the imide skeleton ratio with respect to the organic group that is connected with the Si atom.
Table 2
Embodiment 3 | Embodiment 10 | Embodiment 11 | The reference example | Comparative example 1 | |
Silane compound | ?C | ??N | ??P | ??Q | ?PPSQ-H |
Ratio | ?100% | ??69.7% | ??50.3% | ??30.8% | ?0% |
TGA 5% weight reduces temperature | ?441℃ | ??453℃ | ??430℃ | ??393℃ | ?383℃ |
Hydrolytic resistance | Well | Well | Well | Difference | Well |
As shown in table 2, if the organic group that contains the imide skeleton with respect to the ratio of the organic group that is connected with the Si atom more than or equal to 50%, then TGA 5% weight reduces temperature more than or equal to 400 ℃, has shown excellent thermotolerance, and has shown excellent hydrolytic resistance.That is, if the ratio of organic group of finding to contain the imide skeleton more than or equal to 70% (69.4%~70.4%), then compound exhibits goes out thermotolerance and all excellent characteristic of hydrolytic resistance.Be about 70% if contain the ratio of the organic group of imide skeleton, then compound exhibits goes out thermotolerance and all the most excellent characteristic of hydrolytic resistance.If less than 50%, then compare the balance deterioration between hydrolytic resistance and the thermotolerance in its ratio such as the reference example with embodiment 10 and 11.
Embodiment 12~17 and comparative example 2 and 3
The thermotolerance assessment of<resin combination 〉
By with cresols-novolac type Resins, epoxy (trade(brand)name: EOCN 1020-65, produce by Japanese chemical drug society; Epoxy equivalent (weight) 195g/mol), phenol aralkyl resin (trade(brand)name: HE100C-10, produce by Air-Water, hydroxyl equivalent 118g/mol) mixes and be dissolved in methyl proxitol acetate the equivalent ratio is adjusted into 1.0 mode, obtain mixed resin solution.Silane compound A~D, J, K and PPSQ-H are dissolved in this mixed resin solution, add triphenylphosphine again as curing catalysts, and further append methyl proxitol acetate involatile constituent concentration is adjusted into 60%, thereby obtain resin combination A~H.To be adjusted into 35 weight % and 1.0 weight % respectively with respect to silane compound content and the curing catalysts content ratio in the solid substance of the total amount of solid substance.
Every kind of composition is coated the PTFE film, and (trade(brand)name: Aflex is produced by Asahi Glass society; Film thickness 50 μ m) thus making wet coat-thickness is 200 μ m, afterwards by baking oven in 80 ℃ in air atmosphere dry 5 minutes, in 110 ℃ in air atmosphere 3 minutes, solidified 2 hours in air atmosphere in 180 ℃, thereby obtain to solidify article.
Outward appearance and sense of touch to the film that each obtained are confirmed, and have been carried out the TGA analysis of film.Analysis condition is analyzed identical with the TGA of silane compound.Every kind of film obtaining was placed 100 hours in air atmosphere, 220 ℃ baking oven, and the weight of having studied the film before and after this reduces.
Table 3
Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Comparative example 2 | Comparative example 3 | |
The sample name | Resin combination A | Resin combination B | Resin combination C | Resin combination D | Resin combination E | Resin combination F | Resin combination G | Resin combination H |
Silane compound | ??A | ??B | ??C | ??D | ??J | ??K | ??PPSQ-H | Do not add |
The film outward appearance | Brown deeply, transparent | Brown deeply, transparent | Yellow, transparent | Yellow, transparent | Yellowish, opaque | Yellowish, opaque | White, muddiness | Yellow, transparent |
The film sense of touch | Soft | Soft | Soft | Soft | Soft | Soft | Very easily broken | Frangible |
TGA 5% weight reduces temperature | ??421℃ | ??428℃ | ??419℃ | ??405℃ | ??373℃ | ??360℃ | ??352℃ | ??335℃ |
220 ℃ weight decrement | ??0.15% | ??0.08% | ??0.18% | ??0.21% | ??2.5% | ??1.8% | ??6.8% | ??10.5% |
As shown in table 3, similar to traditional composition epoxy resin, the cured film of not adding the comparative example 2 of silane compound has yellow, transparent and frangible character, and it is opaque and film itself is more frangible than un-added film to have added the film of comparative example of polyphenylene silsesquioxane.On the other hand, dark and keep flexibility transparent and that improve by the film color that resin combination obtained that contains the silane compound in the scope of the present invention.It is opaque but have the flexibility of improvement that utilization contains the prepared film of the resin combination of silane compound J and K.
For thermotolerance, comparative example 2 and 3 film have TGA 5% weight that is not higher than 400 ℃ and reduce temperature, and at 220 ℃ of significant weight decrements that have more than or equal to 5%, and the additive effect of silane compound is less, and TGA 5% weight that the film of embodiment 12~15 has more than or equal to 400 ℃ reduces temperature, and have the lower weight decrement that is no more than 0.3 weight %, thereby shown excellent thermotolerance at 220 ℃.In addition, TGA 5% weight that embodiment 16 and 17 film have more than or equal to 350 ℃ reduces temperature, and has the lower weight decrement that is no more than 2.5 weight % at 220 ℃, thereby has shown excellent thermotolerance.
Embodiment 18~25 and comparative example 4 and 5
The thermotolerance assessment of<resin combination 〉
Above-mentioned silane compound B, C and E are mixed with three kinds of Resins, epoxy, phenols curing agent, maleimide compound, fused silica and the curable epoxide promotor dry type of the amount shown in the table 4, thereby by the hot-rolling kneader mixed mixture fusion and kneading are obtained title complex afterwards.It is 70 ℃ that adjustment kneading condition makes roll surface temperature, and roller fastening pressure (roll fastening pressure) is that 0.5MPa and kneading time are 10 minutes.With the title complex that is obtained be transferred to the template mould (the die cavity distance: thus inside 1mm) with this title complex 180 ℃, 8MPa compression moulding 3 minutes, under the nitrogen circulation condition, placed 7 hours in 180 ℃ subsequently, be the formed body of 1mm thereby obtain thickness.
Each formed body is cut into 10mm * 10mm * 1mm, and under the air cycle condition, placed the weight decrement before and after placing with research 1000 hours in 220 ℃.
The result is displayed in Table 4.In the table 4, addition is all represented with weight part.
Reagent used in the table 4 shows below.
Resins, epoxy: the triphenol based epoxy resin (trade(brand)name: EPPN 501H, produce by Japanese chemical drug society)
The phenol solidifying agent: biphenyl class phenol aralkyl resin (trade(brand)name: MEH 7851SS, produce by Japanese chemical drug society)
Relatively use silane compound: polyphenylene silsesquioxane (trade(brand)name: PPSQ-H, industrial society produces by little westernization)
Maleimide compound (I): 4,4 '-ditan bismaleimides (trade(brand)name: BMI1000 is by big and change into industrial society and produce)
Maleimide compound (II): dihydroxyphenyl propane diphenyl ether bismaleimides (trade(brand)name: BMI4000 is by big and change into industrial society and produce)
Fused silica: trade(brand)name: SO-E2, by Admatechs Co., Ltd. produces
Curing catalyst: triphenylphosphine
As shown in table 4, in the composition of comparative example 4 and 5, added known polyphenylene silsesquioxane, and the weight decrement after leaving standstill in 1000 hours is about 2%, obtained atomic little weight decrement among the embodiment 18~21 and silane compound of the present invention joined, as 0.1%~0.5%.In addition, maleimide compound is joined among the embodiment 22~25, the weight decrement further reduces by 1 order of magnitude, reaches 0.02%~0.08%.
Embodiment 26~29, comparative example 6
The mensuration of the silanol group concentration of<silane compound 〉
The hexamethyldisilazane of the chloroform of every kind of above-mentioned silane compound of 1.0g, 5.0g and 0.1g is joined the glass small bottle container of 10ml, afterwards described container is immersed during vibration bathes.Afterwards, thus mixture is carried out the trimethyl silylization of silanol group in 110 ℃ of dryings in vacuum drying oven.The sample that is obtained is carried out
1H-NMR also recently calculates silanol group concentration ([mole number of Si-OH key]/[mole number of Si-O key]) among silane compound F~I by the integrated value of trimethyl silyl and alpha-methylene.The result is as shown in table 5.
The water absorbability assessment of<resin combination 〉
The weighing equivalence ratio be 1.0 and gross weight be 10g cresols novolac type Resins, epoxy (trade(brand)name: EOCN 1020-65, produce by Japanese chemical drug society; Epoxy equivalent (weight) 195g/mol) and phenol aralkyl resin (trade(brand)name: XLC-4L is produced by Mitsui Chemicals society; Hydroxyl equivalent 168g/mol) and the separable flask of the 100ml that packs into, afterwards with every kind of silane compound F~I and the commercialization polyphenylene silsesquioxane (trade(brand)name: PPSQ-H of 2.5g, industrial society produces by little westernization) dissolving, add triphenylphosphine subsequently as curing catalysts, after 100 ℃ of fusions 5 minutes, every kind of mixture is poured in the glass injection frame that gap thickness is 1mm, thereby leave standstill 7 hours acquisition cured resin plates in 180 ℃.
The cured resin plate is cut into the 20mm square, and under 121 ℃, the condition of the saturation steam of 0.2Mpa, placed 24 hours, assess water absorbability according to the changes in weight before and after placing.The result is as shown in table 5.
Table 5
As shown in table 5, have higher silanol group concentration though silane compound F~I of the present invention compares with comparative example, but even silane compound F~I after handling, also has higher and affinity matrix resin and lower water absorbability in moisture absorption.Find that the silane compound H and the I that do not contain silanol group have shown minimum water absorbability.That is, if embodiment 26 and 27 and embodiment 28 and 29 between show that relatively silanol group concentration is less then anti-water absorbability film is more excellent.
Embodiment 30~35 and comparative example 7~12
The mode that described silane compound L~M is adjusted into 70 weight % with the concentration with involatile constituent is dissolved in toluene according to the ratio shown in the table 6, thus the preparation resin combination.Used material is as follows.
Silane compound L: poly-(γ-(octenyl succinimido) propyl group silsesquioxane)
Silane compound M: poly-(γ-(dodecenyl succinic succinimido) propyl group silsesquioxane)
Commercialization silane compound: polyphenylene silsesquioxane (trade(brand)name: PPSQ-H, industrial society produces by little westernization)
Polyolefine 1: end is the polyolefine (trade(brand)name: Epol is produced by the emerging product of bright dipping society) of hydroxyl
Polyolefine 2: end is the polyolefine (trade(brand)name: Kuraprene LIR410, by Kuraray Co., Ltd. produces) of carboxyl
Polyolefine 3: end is the polyolefine (trade(brand)name: Denalex R-45EPT, produced by NagaseChemtech Ltd.) of epoxy
Solidifying agent 1: hexamethylene diisocyanate
Solidifying agent 2:1,6-hexylene glycol diglycidyl ether
Solidifying agent 3: end is amino polypropylene glycol (trade(brand)name: Jeffamine D400, produced by NitsuiFine Chemicals Inc.)
Curing catalyst 1: dibutyl tin laurate
Curing catalyst 2: triphenylphosphine
<binding property assessment 〉
Wash with the Si wafer immersion acetone of 4-inch and by supersound process, it is the above-mentioned resin combination of 50 μ m that the Si wafer is coated with in solid substance thickness, and it is dry in baking oven under 80 ℃ * 30 minutes condition, and then the condition with 130 ℃ * 30 minutes condition+180 ℃ * 1 hour is handled wafer after in the rare gas element baking oven of wafer transfer in nitrogen atmosphere, thereby obtains to be loaded with the wafer of cured film.Utilize described wafer, carried out the bonding test of crosscut with the binding property of assessment cured film to Si.Assessment result is as shown in table 6.
The water absorbability assessment of<resin combination 〉
With above-mentioned silane compound E and F and commercialization polyphenylene silsesquioxane (trade(brand)name: PPSQ-H, industrial society produces by little westernization) thus the mode that is adjusted into 70 weight % with the concentration with involatile constituent is dissolved in toluene preparation resin combination according to the ratio shown in the table 6.It is the above-mentioned resin combination of 50 μ m that the PET film is coated with in solid substance thickness, and it is dry in baking oven under 80 ℃ * 30 minutes condition, and then the PET film is handled and removed to the condition with 130 ℃ * 30 minutes condition+180 ℃ * 1 hour to the PET film after in the rare gas element baking oven of the PET film being transferred in the nitrogen atmosphere, thereby obtain cured film.
Cured film is cut into the 20mm square, and under the condition of 121 ℃ and 0.2MPa, in saturation steam, placed 24 hours.Recently assess water absorbability according to the changes in weight that leaves standstill the test front and back.Assessment result is as shown in table 6.
<thermotolerance evaluation 〉
Use and assess used identical sample, carried out the TG-DTA analysis with water absorbability.Analysis condition is adjusted into the air cycle of 200mL/min and the rate of heating of 10 ℃/min.Assessment result is as shown in table 6.
Table 6
Shown in comparative example 7~9, do not have excellent binding property though do not contain the composition of silane compound, they also have low heat resistant and high-hygroscopicity.In comparative example 10~12, descend though contain the composition binding property of commercialization silane compound, but thermotolerance improves.On the other hand, in embodiment 30~35, contain silane compound of the present invention composition thermotolerance and anti-water absorbability all improves simultaneously and binding property does not reduce.As a result, contain the relatively confirmation between the resin combination that contains PPSQ-M used in the resin combination of silane compound L and M and the comparative example 10~12, the if tree oil/fat composition is mixed with polyolefin resin then can show very excellent binding property.
The assessment of the dielectric characteristics of<resin combination 〉
Ratio shown in the following table 7 compound of in the separable flask of the 100mL that is equipped with temperature sensor, agitator and reliever, packing into.Be evacuated under the condition of 1kPa at 110 ℃ described compound melting mixing 5 minutes.Pour into mixture in the glass injection frame with 2mm thickness gap and in baking oven, leave standstill 8 hours in 200 ℃, thereby the demoulding subsequently obtains the cured resin plate.Used the silane compound C of preparation in the synthesis example 3.
The cured resin plate is cut into the 30mm square and measures dielectric characteristics.For described test, the TEM formula coaxial resonator that has used AET Inc. to produce; Probe temperature is 23 ℃; And test frequency is 1GHz or 5GHz.
Table 7
The compound of instruction card 7 hereinafter.
Epoxy compounds: phenolic resin varnish (trade(brand)name " EOCN1020-65 " is produced by Japanese chemical drug society)
Phenolic compound: biphenylene phenol aralkyl resin (trade(brand)name " MEH-7851SS " is by clear and change into industry (strain) and produce)
Maleimide compound: meta-phenylene bismaleimide (by producing) with the pure pharmaceutical worker's industry of light (strain)
As shown in table 7, to compare with the composition that does not contain silane compound in the comparative example 13, the resin combination that contains silane compound among the embodiment 36 and 37 has the more specific inductivity of reduction.Particularly, it is remarkable to reduce the effect of tangent of the dielectric loss angle.Along with the ratio of mixture increase of silane compound, can obviously observe the effect that reduces tangent of the dielectric loss angle.Described result shows that the resin combination that contains above-mentioned silane compound and organic resin has as the excellent specific property of dielectric materials with resin combination.
<bonded permanent magnet the assessment of resin combination 〉
Synthesis example 18
35.1g in the four neck flasks of the 300mL that is equipped with agitator, temperature sensor and total condenser, pack in advance with the 3-TSL 8330 of the diglyme and the 30.8g of molecular sieve drying, and when stirring, under with drying nitrogen round-robin condition with mixture heating up to 100 ℃ with the water in the removal system.Next, reaction soln is remained in 100 ℃, in 30 minutes, dividing the 5-norbornylene-2 that adds 28.2g for four times, the 3-dicarboxylic anhydride.After finishing, adding in 9 hours, confirms 5-norbornylene-2, the completely consumed of 3-dicarboxylic anhydride with high performance liquid chromatography.Next, the deionized water of disposable adding 9.3g, temperature is being raise so that by-product carbinol refluxes by total condenser and make reaction system after 95 ℃ keep 10 hours, substitute total condenser with partial condenser, and elevated temperature once more, when reclaiming by-product carbinol and water of condensation, be elevated to 120 ℃ with 3 hours temperature with reaction soln.When temperature reaches 120 ℃, add the pyridine of 1.4g, and according to original state, elevated temperature when reclaiming water of condensation, was elevated to 160 ℃ with 3 hours with temperature once more, make reaction soln remain on this temperature 2 hours and be cooled to room temperature.Reaction soln is the Vandyke brown high viscosity liquid that contains 58.2% involatile constituent, and by the GPC determining molecular weight time, number-average molecular weight is 2340, and weight-average molecular weight is 2570.Carrying out
1H-NMR and
13When C-NMR measures, find that this reaction soln is the polysiloxane compound that contains γ (5-norbornylene-2,3-imide) propyl group.In the 100mL four neck flasks that are equipped with agitator, temperature sensor and total condenser, mix this reaction soln of 24.0g and the cresols phenolic resin varnish (trade(brand)name " EOCN-1020-65 " of 26.0g in 120 ℃, epoxy equivalent (weight): 210g/mol is produced by Japanese chemical drug society).After the diglyme evaporation, make the mixture cooling.As a result, obtained to be the resin combination I of faint yellow transparent solid.Output is 38.3g, and epoxy equivalent (weight) is 323g/mol.
Synthesis example 19
Obtain resin combination J by the mode identical into brown solid with synthesis example 18, difference is to use phenol aralkyl resin (trade(brand)name " MEH-7851-SS ", by MEIWAPLASTIC INDUSTRIES, LTD. production) substituted cresols phenolic resin varnish (trade(brand)name " EOCN-1020-65 ", epoxy equivalent (weight): 210g/mol is produced by Japanese chemical drug society).Output is 38.3g, and hydroxyl equivalent is 312g/mol.
Synthesis example 20
The phenol, the benzo guanamine of 172.2g and 37% formaldehyde solution of 179.2g that in the 1L four neck flasks that are equipped with gas inlet, Dean-Stark water trap and stirring rod, add 432.9g, under the condition of circulating nitrogen gas when 60 ℃ are stirred white casse solution, in this solution, add the ammoniacal liquor of 9mL.Reaction soln become transparent after, solution is heated to 80 ℃.Under agitation, reaction soln was kept 4 hours, subsequently heating once more.Reaction soln is heated to 180 ℃, will about 100 ℃, begins the water that distillatory generated simultaneously and collect in the water trap.With remaining phenol vacuum distilling, thereby afterwards the solution cooling is obtained to be milky white solid resin combination K.Output is 406g, and the thermal softening temperature is 92 ℃, and hydroxyl value is 170g/mol, and mineral compound content is 0%.
Synthesis example 21
The terephthalyl alcohol, the phenol of 687.0g and the tosic acid of 12.6g that in the 2L four neck flasks that are equipped with gas inlet, Dean-Stark water trap and stirring rod, add 302.6g.Subsequently under the condition of circulating nitrogen gas with mixture heating up.About 115 ℃, water begins to generate, and when water is collected in the water trap, solution is heated to 150 ℃ and kept 6 hours.When having collected 79g water, the generation of water finishes.And then, elevated temperature once more under the condition of circulating nitrogen gas.Make solution keep stirring and reach 180 ℃ until temperature.With unreacted phenol vacuum distilling, thereby cooling solution obtains brown semi-solid resin composition L afterwards.Output is 491g, and the thermal softening temperature is 43 ℃, and hydroxyl value is 155g/mol, and mineral compound content is 0%.
Synthesis example 22
Cresols phenolic resin varnish (the trade(brand)name " EOCN-1020-65 " that in the 500mL four neck flasks that are equipped with gas inlet, Dean-Stark water trap and stirring rod, adds 168g, epoxy equivalent (weight): 210g/mol is produced by Japanese chemical drug society) and the glycol diacrylate of 122.3g.With mixture 80 ℃ of stirrings until dissolving fully, add the 4-hydroxyl-2,2 of 0.011g afterwards, 6, the Xiuization tetraphenylphosphoniphenolate of 6-tetramethyl piperidine-1-oxygen and 1.01g, and under the condition of recirculated air, in 110 ℃ with the vinylformic acid that in mixture, dropwise added 59.1g in 2 hours.After the adding, reaction soln was stirred 6 hours in 115 ℃ under the condition of recirculated air.After the acid number of confirming reaction soln is less than or equal to 7mg KOH/g,, reaction soln obtains weak yellow liquid resin combination M thereby being cooled to 40 ℃.Output is 343g, and mineral compound content is 0%, and non-volatile substance content is 64%.
Magnetic powder and resin combination I~M mix and the physical properties assessment with the preparation of sample
By the hot-rolling kneader commercially available SmFeN anisotropic magnetic powder (SUMITOMOMETAL MINING CO., the product of LTD.) and above-mentioned resin combination I~M, curing catalysts and silane coupling agent are mixed.Table 8 has shown the weight ratio of mixture of various compositions.Mediated 5 minutes at 80 ℃ of roller pressures with 0.5MPa.Utilize pressure forming machine that the title complex that is obtained is shaped to the flat board of thickness for 1mm.Utilize freezing crusher by flat board preparation assessment sample subsequently.
The thermotolerance of moulding product
For stable on heating assessment, utilize TG-DTA (ProductName TG-DTA 2000SR, by Bruker Co., Ltd. makes) under the condition of recirculated air, the above-mentioned assessment of weight rate to be determined to be heated with sample.Probe temperature is 150 ℃, 180 ℃ and 200 ℃.Test duration is 24 hours.Sampling interval is 180 seconds.Table 8 has shown the result.
Table 8
Experimental result
In the moulding product of embodiment 38~41, when the moulding product heated under about 150 ℃, weight rate much at one.Thereby the moulding product of embodiment 38~41 looks to have much at one oxidation-resistance.Yet, if with moulding product when higher temperature (180 ℃ and 200 ℃) heats, weight rate increases in embodiment 39~41, thereby oxidation-resistance looks deterioration.In embodiment 38, the weight rate appropriateness increases, and oxidation-resistance reduces slightly.
Claims (31)
1. silane compound with siloxane bond and imide key,
Wherein, described silane compound contains by making at least one organic backbone with imide key be connected the structural unit that forms with the Siliciumatom that forms siloxane bond,
Wherein, described silane compound is limited by a following average group accepted way of doing sth:
XaYbZcSiOd
In the formula,
X is identical or different, and expression is by the group that comprises the organic backbone with imide key shown in the following formula (1);
Z is identical or different, and expression does not have the organic group of imide key;
Y is identical or different, and expression is selected from least a group in the group of being made up of hydrogen atom, hydroxyl, halogen atom and OR group;
R is identical or different, and expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and has substituting group or do not have substituting group;
A is less than or equal to 3 but be not 0 number;
B is 0 or less than 3 number;
C is 0 or less than 3 number;
D is less than 2 but is not 0 number; And
a+b+c+2d=4,
In the formula, R
1Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring;
X and z are identical or different, represent 0~5 integer independently; And
Y is 0 or 1.
2. silane compound as claimed in claim 1,
Wherein, in a described average group accepted way of doing sth,
The coefficient a of X is more than or equal to 0.5.
3. silane compound as claimed in claim 1 or 2,
Wherein, being connected with the Siliciumatom of X and the quantity of the key between the Sauerstoffatom is 3.
4. as each described silane compound in the claim 1~3,
Wherein, forming the Siliciumatom of described siloxane bond and the quantity of the key between the Sauerstoffatom is 3.
5. as each described silane compound in the claim 1~4,
Wherein, the ratio of the silanol base unit weight that is calculated by following formula (α) is less than or equal to 0.1,
[mole number of Si-OH key]/[mole number of Si-O key] (α).
6. as each described silane compound in the claim 1~5,
Wherein, described silane compound has the cage type molecular structure.
7. as each described silane compound in the claim 1~6,
Wherein, the X in the described average group accepted way of doing sth is limited by following formula (2):
In the formula,
R
2~R
5Identical or different, expression is selected from least a group in the group of being made up of hydrogen atom, alkyl, halogen atom and aromatic base independently;
X and z are identical or different, represent 0~5 integer independently; And
Y is 0 or 1.
8. as each described silane compound in the claim 1~6,
Wherein, the X in the described average group accepted way of doing sth is limited by following formula (3):
In the formula,
R
6~R
9And R
6'~R
9' identical or different, expression is selected from least a group in the group of being made up of hydrogen atom, alkyl, halogen atom and aromatic base independently;
X and z are identical or different, represent 0~5 integer independently; And
Y is 0 or 1.
9. as each described silane compound in the claim 1~6,
Wherein, the X in the described average group accepted way of doing sth is limited by following formula (4):
In the formula,
R
10~R
15Identical or different, expression is selected from least a group in the group of being made up of hydrogen atom, alkyl, halogen atom and aromatic base independently;
X and z are identical or different, represent 0~5 integer independently; And
Y is 0 or 1.
10. as each described silane compound in the claim 1~6,
Wherein, the X in the described average group accepted way of doing sth is limited by following formula (5):
In the formula,
R
16~R
21Identical or different, expression is selected from least a group in the group of being made up of hydrogen atom, alkyl, halogen atom and aromatic base independently;
X and z are identical or different, represent 0~5 integer independently; And
Y is 0 or 1.
11. as each described silane compound in the claim 1~6,
Wherein, the X in the described average group accepted way of doing sth is limited by following formula (6):
In the formula,
R
22~R
25And R
22'~R
25' identical or different, expression is selected from least a group in the group of being made up of hydrogen atom, alkyl, halogen atom and aromatic base independently;
X and z are identical or different, represent 0~5 integer independently; And
Y is 0 or 1.
12. as each described silane compound in the claim 1~6,
Wherein, the X in the described average group accepted way of doing sth is limited by following formula (7):
In the formula,
R
26Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring.
13. the silane compound with siloxane bond and amido bond,
Wherein, described silane compound is limited by a following average group accepted way of doing sth:
X’
aY
bZ
cSiO
d
In the formula,
X ' is identical or different, and expression has the organic backbone of amido bond;
Z is identical or different, and expression does not have the organic backbone of amido bond;
Y is identical or different, and expression is selected from least a group in the group of being made up of hydrogen atom, hydroxyl, halogen atom and OR group;
R is identical or different, and expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and has substituting group or do not have substituting group;
A is less than or equal to 3 but be not 0 number;
B is 0 or less than 3 number;
C is 0 or less than 3 number;
D is less than 2 but is not 0 number; And
A+b+c+2d=4, and the X ' in the described average group accepted way of doing sth is limited by following formula (8):
In the formula,
R
27Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring;
X and z are identical or different, represent 0~5 integer independently; And
Y is 0 or 1.
14. silane compound as claimed in claim 13,
Wherein, in a described average group accepted way of doing sth,
The coefficient a of X ' is more than or equal to 0.5.
15. silane compound as claimed in claim 14,
Wherein, being connected with the Siliciumatom of X ' and the quantity of the key between the Sauerstoffatom is 3.
16. as each described silane compound in the claim 13~15,
Wherein, forming the Siliciumatom of described siloxane bond and the quantity of the key between the Sauerstoffatom is 3.
17. as each described silane compound in the claim 13~16,
Wherein, the ratio of the silanol base unit weight that is calculated by following formula (α) is less than or equal to 0.1,
[mole number of Si-OH key]/[mole number of Si-O key] (α).
18. as each described silane compound in the claim 13~17,
Wherein, described silane compound has the cage type molecular structure.
19. the silane compound with amido bond,
Wherein, described silane compound is limited by following formula (9):
In the formula,
R
28Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring;
R
29Identical or different, the expression organic group;
R
30Identical or different, expression is selected from by hydrogen atom, hydroxyl, halogen atom and OR
30' at least a group in the group formed of group;
R
30' identical or different, expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and has substituting group or do not have substituting group;
X and z are identical or different, represent 0~5 integer independently;
Y is 0 or 1; And
P is 0~2 integer.
20. the silane compound with imide key,
Wherein, described silane compound is limited by following formula (10):
In the formula,
R
31Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring;
R
32Identical or different, the expression organic group;
R
33Identical or different, expression is selected from by hydrogen atom, hydroxyl, halogen atom and OR
33' at least a group in the group formed of group;
R
33' identical or different, expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and has substituting group or do not have substituting group;
X and z are identical or different, represent 0~5 integer independently;
Y is 0 or 1; And
Q is 0~2 integer.
21. silane compound production method of producing each described silane compound in the claim 1~12.
22. silane compound production method as claimed in claim 21,
Wherein, described production method comprises that the intermediate that the silane compound that is limited by a following average group accepted way of doing sth is formed carries out the step of imidization:
X’
aY
bZ
cSiO
d
In the formula,
X ' is identical or different, and expression has the organic backbone of amido bond;
Z is identical or different, and expression does not have the organic backbone of amido bond;
Y is identical or different, and expression is selected from least a group in the group of being made up of hydrogen atom, hydroxyl, halogen atom and OR group;
R is identical or different, and expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and has substituting group or do not have substituting group;
A is less than or equal to 3 but be not 0 number;
B is 0 or less than 3 number;
C is 0 or less than 3 number;
D is less than 2 but is not 0 number; And
A+b+c+2d=4, and
X ' in the described average group accepted way of doing sth is limited by following formula (8):
In the formula,
R
27Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring;
X and z are identical or different, represent 0~5 integer independently; And
Y is 0 or 1.
23. silane compound production method as claimed in claim 22,
Wherein, described production method comprises that the intermediate that the silane compound that is limited by following formula (9) is formed is hydrolyzed and the step of polycondensation:
In the formula,
R
28Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring;
R
29Identical or different, the expression organic group;
R
30Identical or different, expression is selected from by hydrogen atom, hydroxyl, halogen atom and OR
30' at least a group in the group formed of group;
R
30' identical or different, expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and has substituting group or do not have substituting group;
X and z are identical or different, represent 0~5 integer independently;
Y is 0 or 1; And
P is 0~2 integer.
24. silane compound production method as claimed in claim 21,
Wherein, described production method comprises that the intermediate that the silane compound that is limited by following formula (10) is formed is hydrolyzed and the step of polycondensation:
In the formula,
R
31Expression is selected from least a structure in the group of being made up of aromatic nucleus, heterocycle and alicyclic ring;
R
32Identical or different, the expression organic group;
R
33Identical or different, expression is selected from by hydrogen atom, hydroxyl, halogen atom and OR
33' at least a group in the group formed of group;
R
33' identical or different, expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and has substituting group or do not have substituting group;
X and z are identical or different, represent 0~5 integer independently;
Y is 0 or 1; And
Q is 0~2 integer.
25. silane compound production method as claimed in claim 24,
Wherein, described production method comprises that the compound that limits from following formula (11) obtains the step of the intermediate be made up of the silane compound that formula (10) limits:
In the formula,
A represents halogen atom or isocyanate group;
R
34Identical or different, the expression organic group;
R
35Identical or different, expression is selected from by hydrogen atom, hydroxyl, halogen atom and OR
35' at least a group in the group formed of group;
R
35' identical or different, expression is selected from least a group in the group of being made up of alkyl, acyl group, aryl and unsaturated aliphatic residue, and has substituting group or do not have substituting group;
X and z are identical or different, represent 0~5 integer independently;
Y is 0 or 1; And
R is 0~2 integer.
26. a resin combination, described resin combination comprise each described silane compound and organic resin in the claim 1~20.
27. resin combination as claimed in claim 26,
Wherein, described resin combination is the semiconductor device resin combination.
28. a semiconductor-encapsulating material, described semiconductor-encapsulating material comprise the described semiconductor device resin combination of claim 27.
29. a semiconductor mounting substrate, described semiconductor mounting substrate utilize the described semiconductor device of claim 27 to make with resin combination.
30. resin combination as claimed in claim 26,
Wherein, described resin combination is the dielectric materials resin combination.
31. resin combination as claimed in claim 26,
Wherein, described resin combination is the bonded permanent magnet resin combination.
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JP149576/2007 | 2007-06-05 | ||
JP271791/2007 | 2007-10-18 |
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WO2020168542A1 (en) * | 2019-02-22 | 2020-08-27 | 湖州五爻硅基材料研究院有限公司 | Method for preparing spherical or angular powder filler, spherical or angular powder filler obtained thereby and application thereof |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001100417A (en) * | 1999-09-28 | 2001-04-13 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JP2001100418A (en) * | 1999-09-28 | 2001-04-13 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JP2007031321A (en) * | 2005-07-25 | 2007-02-08 | Shin Etsu Chem Co Ltd | Method for producing imide bonded with organosiloxane, triorganosilyl ester of amic acid bonded with organosiloxane, and method for manufacturing the same |
-
2008
- 2008-02-07 CN CN200880004127A patent/CN101627043A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001100417A (en) * | 1999-09-28 | 2001-04-13 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JP2001100418A (en) * | 1999-09-28 | 2001-04-13 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JP2007031321A (en) * | 2005-07-25 | 2007-02-08 | Shin Etsu Chem Co Ltd | Method for producing imide bonded with organosiloxane, triorganosilyl ester of amic acid bonded with organosiloxane, and method for manufacturing the same |
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