TW201504251A - Borazine compound, borazine composition, and cross-linked borazine structure - Google Patents
Borazine compound, borazine composition, and cross-linked borazine structure Download PDFInfo
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- TW201504251A TW201504251A TW103111717A TW103111717A TW201504251A TW 201504251 A TW201504251 A TW 201504251A TW 103111717 A TW103111717 A TW 103111717A TW 103111717 A TW103111717 A TW 103111717A TW 201504251 A TW201504251 A TW 201504251A
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- borazine
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- compound
- hydrogen atom
- borazine compound
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- -1 Borazine compound Chemical class 0.000 title claims abstract description 102
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 23
- 239000012776 electronic material Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 125000001424 substituent group Chemical group 0.000 claims description 29
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 6
- 239000004971 Cross linker Substances 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- AAKRRFGGZYOTQQ-UHFFFAOYSA-N [B].[B].[N] Chemical compound [B].[B].[N] AAKRRFGGZYOTQQ-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 12
- 125000004122 cyclic group Chemical group 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 230000004888 barrier function Effects 0.000 abstract description 6
- 239000011229 interlayer Substances 0.000 abstract description 5
- 239000003566 sealing material Substances 0.000 abstract description 5
- 125000005462 imide group Chemical group 0.000 abstract 1
- 229910052796 boron Inorganic materials 0.000 description 52
- 150000004060 quinone imines Chemical group 0.000 description 34
- 229910052757 nitrogen Inorganic materials 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- 238000001816 cooling Methods 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 238000000859 sublimation Methods 0.000 description 7
- 230000008022 sublimation Effects 0.000 description 7
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 7
- PJLCCHSTNPFKPU-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;ruthenium(3+) Chemical compound [Ru+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PJLCCHSTNPFKPU-UHFFFAOYSA-K 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 150000003613 toluenes Chemical class 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 150000008422 chlorobenzenes Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 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 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004151 quinonyl group Chemical group 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 2
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 2
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- FKAWETHEYBZGSR-UHFFFAOYSA-N 3-methylidenepyrrolidine-2,5-dione Chemical compound C=C1CC(=O)NC1=O FKAWETHEYBZGSR-UHFFFAOYSA-N 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical group C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- YSMSEUODXDWEKM-UHFFFAOYSA-N NN1BNBNB1 Chemical compound NN1BNBNB1 YSMSEUODXDWEKM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KPSZQYZCNSCYGG-UHFFFAOYSA-N [B].[B] Chemical compound [B].[B] KPSZQYZCNSCYGG-UHFFFAOYSA-N 0.000 description 1
- VUAFMBNGAGWGIS-UHFFFAOYSA-K [Y+3].[O-]N=O.[O-]N=O.[O-]N=O Chemical group [Y+3].[O-]N=O.[O-]N=O.[O-]N=O VUAFMBNGAGWGIS-UHFFFAOYSA-K 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 125000005543 phthalimide group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- UGQZLDXDWSPAOM-UHFFFAOYSA-N pyrrolo[3,4-f]isoindole-1,3,5,7-tetrone Chemical compound C1=C2C(=O)NC(=O)C2=CC2=C1C(=O)NC2=O UGQZLDXDWSPAOM-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
Description
本發明係關於耐熱性、透明性、介電特性、熱傳導性、氣體障壁性、硬度、耐藥品性、耐候性、絕緣性及低折射性優異之新穎環硼氮烷化合物、環硼氮烷組成物、環硼氮烷交聯體及使用該等之電子材料者。此環硼氮烷化合物不是交聯其本身，或藉由與各種交聯劑進行反應，可賦予耐熱性、透明性、介電特性、熱傳導性、氣體障壁性、硬度、耐藥品性、耐候性、絕緣性及低折射性優異之材料，可使用在層合板、層間絕緣膜、密封材料等之電子材料、塗料、接著劑等各種用途。 The present invention relates to a novel borazine compound and a borazine composition which are excellent in heat resistance, transparency, dielectric properties, thermal conductivity, gas barrier properties, hardness, chemical resistance, weather resistance, insulation, and low refractive index. And borax alkane crosslinkers and those using such electronic materials. The borazine compound is not crosslinked by itself or by reacting with various crosslinking agents to impart heat resistance, transparency, dielectric properties, thermal conductivity, gas barrier properties, hardness, chemical resistance, and weather resistance. A material excellent in insulation and low refractive index can be used in various applications such as an electronic material such as a laminate, an interlayer insulating film, and a sealing material, a paint, and an adhesive.
環硼氮烷化合物係耐熱性、透明性、介電特性、熱傳導性、氣體障壁性、硬度、耐藥品性、耐候性、電荷輸送性優異，可期待被作為高耐熱材料、低介電材料、高放熱材料及低折射材料。例如進行具有無取代及鹵基之化合物(專利文獻1)、胺基環硼氮烷(專利文獻2及3)、聚胺基環硼氮烷(專利文獻4)、烷基環硼氮烷(專利文獻5)、具有亞甲基或乙炔基之化合物(專利文 獻6)、具有多環芳香族基之化合物(專利文獻7)等之各式各樣研究。然而，上述具有無取代體及鹵基之化合物容易水解。上述具有胺基環硼氮烷、烷基環硼氮烷及多環芳香族之化合物雖已改善水解性，但由於有昇華性且溶劑溶解性亦低故操作困難。上述具有聚胺基環硼氮烷及亞甲基或乙炔基之化合物雖提昇操作性，但溶劑溶解性不夠充分，於製膜性有缺點。 The borazine compound is excellent in heat resistance, transparency, dielectric properties, thermal conductivity, gas barrier properties, hardness, chemical resistance, weather resistance, and charge transportability, and can be expected to be used as a high heat resistant material or a low dielectric material. Highly exothermic materials and low refractive materials. For example, a compound having an unsubstituted and halogen group (Patent Document 1), an amine borazine (Patent Documents 2 and 3), a polyamino borazine (Patent Document 4), and an alkyl borazine are used. Patent Document 5), a compound having a methylene group or an ethynyl group (patent text) 6) A variety of studies such as a compound having a polycyclic aromatic group (Patent Document 7). However, the above compound having an unsubstituted body and a halogen group is easily hydrolyzed. Although the above-mentioned compound having an aminoborazine, an alkylborazine and a polycyclic aromatic has improved hydrolysis property, it is difficult to handle because of sublimation property and low solvent solubility. The compound having a polyaminoborazine and a methylene or ethynyl group has improved handleability, but solvent solubility is insufficient, and there are disadvantages in film formability.
[專利文獻1]日本特開昭61-10090號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 61-10090
[專利文獻2]日本特開平1-290510號公報 [Patent Document 2] Japanese Patent Laid-Open No. 1-290510
[專利文獻3]日本特開平7-292120號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 7-292120
[專利文獻4]日本特開2008-239796號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-239796
[專利文獻5]日本特開2005-104869號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2005-104869
[專利文獻6]日本特開2005-85962號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2005-85962
[專利文獻7]日本特開2005-170857號公報 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2005-170857
如上述，以往之環硼氮烷化合物有耐水解性等之穩定性或操作性、製膜性等之加工性問題。 As described above, the conventional borazine compound has problems such as stability such as hydrolysis resistance, workability, and film formability.
本發明者等鑑於在上述以往技術之實狀，發明具有環狀醯亞胺基之環硼氮烷化合物及上述環硼氮烷化 合物與交聯劑的交聯體。 The inventors of the present invention have invented the borazine compound having a cyclic quinone imine group and the above borazine in view of the above-described conventional techniques. A crosslinked body of a compound and a crosslinking agent.
亦即，本發明係關於下述一般式(1)所示之環硼氮烷化合物。 That is, the present invention relates to a borazine compound represented by the following general formula (1).
式中，A1~A3分別獨立表示氫原子或一價之取代基，Y1及Y2分別獨立表示氫原子或一價之取代基，Z1及Z2分別獨立表示氫原子或一價之取代基，可彼此鍵結而形成環。虛線部分表示單鍵或雙鍵。 In the formula, A 1 to A 3 each independently represent a hydrogen atom or a monovalent substituent, and Y 1 and Y 2 each independently represent a hydrogen atom or a monovalent substituent, and Z 1 and Z 2 each independently represent a hydrogen atom or a monovalent group. The substituents may be bonded to each other to form a ring. The dotted line indicates a single bond or a double bond.
又，本發明係關於下述一般式(2)或一般式(3)所示之環硼氮烷化合物。 Further, the present invention relates to a borazine compound represented by the following general formula (2) or general formula (3).
式中，A1~A3、Y1~Y2、Z1~Z2與一般式(1)相同意義。Z3~Z6分別獨立表示氫原子或一價之取代基，可彼此鍵結而形成環，虛線部分表示單鍵或雙鍵。 In the formula, A 1 to A 3 , Y 1 to Y 2 , and Z 1 to Z 2 have the same meanings as in the general formula (1). Z 3 to Z 6 each independently represent a hydrogen atom or a monovalent substituent, which may be bonded to each other to form a ring, and the dotted line portion represents a single bond or a double bond.
又，本發明其特徵係關於含有上述之環硼氮烷化合物與交聯劑之環硼氮烷組成物。 Further, the present invention relates to a borazine composition comprising the above borazine compound and a crosslinking agent.
又，本發明其特徵係關於使上述之環硼氮烷組成物進行交聯而成之環硼氮烷交聯體。 Further, the present invention relates to a borazine-lined crosslinked body obtained by crosslinking the above borazine composition.
上述之環硼氮烷化合物適合作為電子材料用。 The above borazine compound is suitable for use as an electronic material.
本發明之環硼氮烷化合物由於具有醯亞胺基，故不僅穩定性、加工性優異，且耐熱性、透明性、介電特性、熱傳導性、氣體障壁性、硬度、耐藥品性、耐候性、絕緣性及低折射性優異。又，藉由與各種交聯劑進行反應，可賦予耐熱性、透明性、介電特性、熱傳導性、氣 體障壁性、硬度、耐藥品性、耐候性、絕緣性及低折射性優異之材料，可使用於層合板、層間絕緣膜、密封材料等之電子材料、塗料、接著劑等各種用途。 Since the borazine compound of the present invention has a quinone imine group, it is excellent not only in stability and workability, but also heat resistance, transparency, dielectric properties, thermal conductivity, gas barrier properties, hardness, chemical resistance, and weather resistance. Excellent in insulation and low refractive index. Moreover, by reacting with various crosslinking agents, heat resistance, transparency, dielectric properties, thermal conductivity, and gas can be imparted. A material excellent in physical barrier properties, hardness, chemical resistance, weather resistance, insulation, and low refractive index can be used for various applications such as an electronic material such as a laminate, an interlayer insulating film, and a sealing material, a coating material, and an adhesive.
[圖1]係本發明之環硼氮烷化合物a-4之1H-NMR光譜。 Fig. 1 is a 1 H-NMR spectrum of the borazine compound a-4 of the present invention.
[圖2]係本發明之環硼氮烷化合物a-5之1H-NMR光譜。 Fig. 2 is a 1 H-NMR spectrum of the borazine compound a-5 of the present invention.
首先，對於本發明之環硼氮烷化合物進行說明。 First, the borazine compound of the present invention will be described.
本發明之環硼氮烷化合物係上述一般式(1)所示。作為較佳之環硼氮烷化合物為上述一般式(2)~(3)所示之化合物。 The borazine compound of the present invention is represented by the above general formula (1). Preferred borazine compounds are the compounds represented by the above general formulas (2) to (3).
於此，A1~A3分別獨立表示氫原子或一價之取代基，Y1及Y2分別獨立表示氫原子或一價之取代基，Z1~Z6分別獨立表示氫原子或一價之取代基，可彼此鍵結而形成環。尚且，一般式(1)~(3)中，共通之記號具有相同意義。 Herein, A 1 to A 3 each independently represent a hydrogen atom or a monovalent substituent, and Y 1 and Y 2 each independently represent a hydrogen atom or a monovalent substituent, and Z 1 to Z 6 each independently represent a hydrogen atom or a monovalent group. The substituents may be bonded to each other to form a ring. Moreover, in the general formulas (1) to (3), the common symbols have the same meaning.
A1~A3為一價之取代基時，此取代基雖並未特別限制，但例如可列舉烷基、芳基、芳烷基、胺基、烷 氧基、羥基、羧基、乙烯基等。較佳係A1~A3為氫原子、烷基、芳基、芳烷基、或胺基，更佳為C1~C6之烷基、苯基、萘基、苯基甲基、苯基乙基、萘甲基、萘乙基或胺基，再更佳為苯基或萘基。此等之一價之取代基可進一步鍵結一價之取代基，較佳為C1~C12之烷基或苯基，更佳為C1~C6之烷基或苯基。 When A 1 to A 3 are a monovalent substituent, the substituent is not particularly limited, and examples thereof include an alkyl group, an aryl group, an arylalkyl group, an amine group, an alkoxy group, a hydroxyl group, a carboxyl group, a vinyl group, and the like. . Preferably, A 1 to A 3 are a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or an amine group, more preferably an alkyl group of C 1 to C 6 , a phenyl group, a naphthyl group, a phenylmethyl group or a benzene group. Further, a ethyl group, a naphthylmethyl group, a naphthylethyl group or an amine group is more preferably a phenyl group or a naphthyl group. These one-valent substituents may further bond a monovalent substituent, preferably a C 1 -C 12 alkyl group or a phenyl group, more preferably a C 1 -C 6 alkyl group or a phenyl group.
Y1及Y2為一價之取代基時，此取代基雖並未 特別限制，但例如可列舉烷基、芳基、芳烷基、胺基、烷氧基、羥基、羧基、乙烯基、醯亞胺基等。較佳係Y1及Y2為氫原子、烷基、芳基、芳烷基、胺基、醯亞胺基，更佳為C1~C6之烷基、苯基、萘基、苯基甲基、苯基乙基、萘甲基、萘乙基、胺基或醯亞胺基，再更佳為醯亞胺基。醯亞胺基時，特佳為醯亞胺基本身形成環構造。 When Y 1 and Y 2 are a monovalent substituent, the substituent is not particularly limited, and examples thereof include an alkyl group, an aryl group, an arylalkyl group, an amine group, an alkoxy group, a hydroxyl group, a carboxyl group, and a vinyl group.醯imino group and the like. Preferably, Y 1 and Y 2 are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an amine group, a quinone imine group, more preferably a C 1 -C 6 alkyl group, a phenyl group, a naphthyl group or a phenyl group. Methyl, phenylethyl, naphthylmethyl, naphthylethyl, amine or quinone imine, more preferably quinone. In the case of a quinone imine group, it is particularly preferred that the quinone imine form a ring structure.
於此，所謂醯亞胺基係下述式(b)所示之構造。 Here, the quinone imine group is a structure represented by the following formula (b).
R1及R2分別獨立為氫原子、C1~C12之烷基、苯基或萘基。又，R1、R2及N原子可形成環。較佳為R1與R2鍵結，形成包含N原子之5員環的構造。 R 1 and R 2 each independently represent a hydrogen atom, a C 1 -C 12 alkyl group, a phenyl group or a naphthyl group. Further, R 1 , R 2 and N atoms may form a ring. Preferably, R 1 and R 2 are bonded to each other to form a 5-membered ring containing N atoms.
具有較佳環構造之醯亞胺基係下述式(a)所示。以下，將具有式(a)所示之環構造之醯亞胺基稱為 環狀醯亞胺基(a)。 The quinone imine group having a preferred ring structure is represented by the following formula (a). Hereinafter, the quinone imine group having the ring structure represented by the formula (a) is referred to as Cyclic quinone imine (a).
式中，Z獨立表示氫原子或一價之取代基，可彼此鍵結而形成環。虛線部分表示單鍵或雙鍵。此Z被理解為對應於上述一般式(1)~(3)之Z1~Z6之任一種，與Z1~Z6具有相同意義。一般式(1)~(3)之環硼氮烷化合物係具有1、2或3個環狀醯亞胺基(a)。 In the formula, Z independently represents a hydrogen atom or a monovalent substituent which may be bonded to each other to form a ring. The dotted line indicates a single bond or a double bond. This Z is understood to correspond to any of Z 1 to Z 6 of the above general formulas (1) to (3), and has the same meaning as Z 1 to Z 6 . The borazine compound of the general formulae (1) to (3) has 1, 2 or 3 cyclic quinone imine groups (a).
一般式(1)~(3)中之Z1~Z6雖分別獨立為氫或一價之取代基，但可鍵結於此等而形成環。又，藉由Z1~Z6之複數可形成縮合環。一價之取代基較佳為烷基或苯基，更佳為C1~C6之烷基或苯基。形成縮合環時，此縮合環較佳為苯環、環己烯環、降莰烯環、或甲基降莰烯環為與環狀醯亞胺基之醯亞胺環縮合之構造的縮合環。 Although Z 1 to Z 6 in the general formulae (1) to (3) are each independently hydrogen or a monovalent substituent, they may be bonded to each other to form a ring. Further, a condensed ring can be formed by a complex number of Z 1 to Z 6 . The monovalent substituent is preferably an alkyl group or a phenyl group, more preferably a C 1 to C 6 alkyl group or a phenyl group. When the condensed ring is formed, the condensed ring is preferably a condensed ring having a benzene ring, a cyclohexene ring, a norbornene ring, or a methyl norbornene ring condensed with a cyclic quinone imine group. .
一般式(1)~(3)中取代Z1~Z6之環狀醯亞胺基中，虛線表示單鍵或雙鍵。單鍵時，鍵結Z1~Z6之碳亦可與1個氫原子鍵結。 In the general formula (1) to (3), in the cyclic quinone imine group which replaces Z 1 to Z 6 , a broken line indicates a single bond or a double bond. At the single bond, the carbon of the bond Z 1 to Z 6 may also be bonded to one hydrogen atom.
醯亞胺基本身為形成環構造時，下述之構造為較佳之例示。為馬來醯亞胺基、苯二甲酸醯亞胺基、檸康酸醯亞胺基、納迪克酸(Nadic acid)醯亞胺基、或甲 基納迪克酸醯亞胺基。此等之構造可進一步具有一價之取代基。此等之一價之取代基較佳為烷基或苯基，更佳為C1~C6之烷基或苯基。 When the quinone imine is basically formed into a ring structure, the following structure is a preferred example. It is a maleidino group, a phthalimide group, a quinone iodide group, a nadic acid quinone imine group, or a methyl nadic acid ruthenium group. Such configurations may further have a monovalent substituent. The one-valent substituent is preferably an alkyl group or a phenyl group, more preferably a C 1 -C 6 alkyl group or a phenyl group.
本發明之環硼氮烷組成物係包含上述環硼氮 烷化合物與任意之交聯劑。尤其是上述環硼氮烷化合物之環狀醯亞胺基(a)為具有碳-碳不飽和鍵(雙鍵或三鍵)時，與任意之交聯劑反應而形成低聚物。碳-碳不飽和鍵可具有環狀醯亞胺基本身，可具有取代其之取代基Z1~Z6。 The borazine component of the present invention comprises the above borazine compound and any crosslinking agent. In particular, when the cyclic quinone imine group (a) of the above borazine compound has a carbon-carbon unsaturated bond (double bond or triple bond), it reacts with any crosslinking agent to form an oligomer. The carbon-carbon unsaturated bond may have a cyclic quinone imine basic body and may have a substituent Z 1 to Z 6 substituted therewith.
於此，交聯劑係例如具有胺基、醯亞胺基、 酚性羥基、氰酸酯基之化合物。又，交聯劑可併用複數之種類。作為交聯劑，使用具有二官能以上之胺基、醯亞胺基、酚性羥基、氰酸酯基之化合物、或具有2以上碳-碳不飽和鍵之化合物時，環硼氮烷交聯體成為低聚物。於此，作為交聯劑，使用二官能以上胺基、具有2以上碳-碳不飽和鍵之環狀醯亞胺基、二官能以上之酚性羥基、具有氰酸酯基之化合物時，上述環硼氮烷化合物之碳-碳不飽和鍵反應。據此，此情況，環硼氮烷化合物係具有此等之官能基與反應性之碳-碳不飽和鍵。 Here, the crosslinking agent has, for example, an amine group, a quinone imine group, A compound of a phenolic hydroxyl group or a cyanate group. Further, the crosslinking agent may be used in combination of plural types. When a compound having a difunctional or higher amine group, a quinone imine group, a phenolic hydroxyl group, a cyanate group, or a compound having 2 or more carbon-carbon unsaturated bonds is used as the crosslinking agent, the borazine is crosslinked. The body becomes an oligomer. Here, when a difunctional or higher amine group, a cyclic quinone imine group having two or more carbon-carbon unsaturated bonds, a difunctional or higher phenolic hydroxyl group, or a compound having a cyanate group is used as the crosslinking agent, The carbon-carbon unsaturated bond of the borazine compound reacts. Accordingly, in this case, the borazine compound has such a functional group and a reactive carbon-carbon unsaturated bond.
又，上述環硼氮烷組成物中，可包含三苯基 膦、2-乙基-4甲基咪唑、辛酸鋅等之交聯促進劑(以下亦稱為「促進劑」)。 Further, the above borazine composition may include triphenyl group A crosslinking accelerator (hereinafter also referred to as "accelerator") such as phosphine, 2-ethyl-4-methylimidazole or zinc octoate.
又，可將本發明之環硼氮烷化合物單獨或上述環硼氮烷組成物成為使其交聯之環硼氮烷交聯體。作為 交聯方法可列舉熱硬化、光硬化。 Further, the borazine compound of the present invention alone or the above borazine composition may be a crosslinked borazine. As Examples of the crosslinking method include thermal curing and photo hardening.
又，上述之環硼氮烷化合物及環硼氮烷交聯體可分散於聚合物基體中。 Further, the above borazine compound and the borazine alkaloid crosslinkable body may be dispersed in the polymer matrix.
對於本發明之環硼氮烷化合物之製造方法之一例說明於以下。 An example of a method for producing the borazine compound of the present invention will be described below.
本發明之醯亞胺基含有環硼氮烷化合物係例如如下述反應式(4)所示，可藉由醯亞胺化B,B’,B”-三氯環硼氮烷(a-1)予以製造。此B,B’,B”-三氯環硼氮烷(a-1)係由三氯化硼與胺基化合物之縮合反應而製造。此時，可適當參酌“Organoboron-nitrogen Compounds.I.The Reaction of Boron Chloride with Aniline”,Reuben G.Jones,Corliss R.Kinney；Journal of the American Chemical Society,61,p1378-1381(1939)或E.L.Muetterties ed.,K.Niedenzu et al.,Inorg.Synth.,10,142(1967)之文獻進行製造。 The quinone imine group of the present invention contains a borazine compound, for example, as shown in the following reaction formula (4), which can be imidized by B, B', B"-trichloroborazine (a-1). This B, B', B"-trichloroborazine (a-1) is produced by a condensation reaction of boron trichloride with an amine compound. At this time, "Organoboron-nitrogen Compounds. I. The Reaction of Boron Chloride with Aniline", Reuben G. Jones, Corliss R. Kinney; Journal of the American Chemical Society, 61, p1378-1381 (1939) or EL can be appropriately considered. Manufactured by Muetterties ed., K. Niedenzu et al., Inorg. Synth., 10, 142 (1967).
進而使B,B’,B”-三氯環硼氮烷(a-1)與醯亞胺化合物進行反應而得到含有醯亞胺基之環硼氮烷化合物(a-2)。 Further, B, B', B"-trichloroborazine (a-1) is reacted with a quinone imine compound to obtain a quinone group-containing borazine compound (a-2).
反應式(4)係3分子取代醯亞胺基於環硼氮烷環，且雖對於鍵結於環硼氮烷環之硼原子之取代基為完全相同之含有醯亞胺基之環硼氮烷化合物例示，但藉由使不具有胺基化合物等之醯亞胺基之混合物進行反應，可製造1分子或2分子取代醯亞胺基於環硼氮烷環之含有醯亞胺基之環硼氮烷化合物。又，藉由使醯亞胺基作為複數種類之混 合物進行反應，鍵結於環硼氮烷環之硼原子之3分子的取代基可成為分別不同之含有醯亞胺基之環硼氮烷化合物。 The reaction formula (4) is a 3-mole-substituted quinone imine based on a borazine ring, and although the substituent bonded to the boron atom of the borazine ring is the same quinone group-containing borazine The compound is exemplified, but by reacting a mixture of a quinone imine group having no amine compound or the like, one or two molecules of a substituted quinone imine based on a bororeazide ring containing a quinone imine group can be produced. Alkane compound. Also, by using a quinone imine group as a mixture of plural types The compound is reacted, and the substituent of 3 molecules bonded to the boron atom of the borazine ring may be a borazine compound having a different quinone imine group.
B,B’,B”-三氯環硼氮烷之合成與其醯亞胺化反應可分成二階段之步驟，亦可連續進行反應。 The synthesis of B, B', B"-trichloroborazine and its hydrazine imidization reaction can be carried out in two stages, and the reaction can be carried out continuously.
式中，A1分別獨立，與在一般式(1)之A1~A3相同，Z1及Z2分別獨立，與在一般式(1)之Z1及Z2相同。虛線部分表示單鍵或雙鍵。 Wherein, A 1 is independently, the same as A in the general formula (1) of 1 ~ A 3, Z 1 and Z 2 are each independently, and in general formula (1) the same as Z 1 and Z 2. The dotted line indicates a single bond or a double bond.
上述反應式(4)中，可取代三氯化硼改使用三氟化硼、三溴化硼或三碘化硼使其反應。該情況，取代B,B’,B”-三氯環硼氮烷，而得到B,B’,B”-三氟環硼氮烷、B,B’,B”-三溴環硼氮烷或B,B’,B”-三碘環硼氮烷。此等即使進行醯亞胺化反應亦可製造含有醯亞胺基之環硼氮烷化合物(a-2)。惟，鹵基環硼氮烷合成時，從於溶液狀態操作之容易性，反應中所產生之廢氣體(未反應之氯化硼 及氯化氫)於系統外可容易處理之理由，以使用三氯化硼之B,B’,B”-三氯環硼氮烷為佳。以下，以B,B’,B”-三氯環硼氮烷代表說明。 In the above reaction formula (4), boron trichloride, boron tribromide or boron triiodide may be used instead of boron trichloride to cause a reaction. In this case, instead of B, B', B"-trichloroborazine, B, B', B"-trifluoroboroxine, B, B', B"-tribromoborazine Or B, B', B"-triiodoboroxane. Such a borazine compound (a-2) containing a quinone imine group can be produced even if the ruthenium imidization reaction is carried out. However, when the halogen borazine is synthesized, the effluent generated from the reaction is easy to operate from the solution state (unreacted boron chloride) And hydrogen chloride) can be easily handled outside the system, preferably B, B', B"-trichloroborazine using boron trichloride. Hereinafter, B, B', B"-trichlorocyclohexane The borazane represents the description.
作為與B,B’,B”-三氯環硼氮烷反應之醯亞胺 化合物，可列舉以下者。馬來醯亞胺、檸康酸醯亞胺、衣康酸醯亞胺、苯二甲酸醯亞胺、納迪克酸醯亞胺、納迪克酸醯亞胺、甲基納迪克酸醯亞胺、cis-4-環己烯-1,2-二羧酸醯亞胺、cis-1,2-環己烷二羧酸醯亞胺、烯丙基納迪克酸醯亞胺等之單醯亞胺化合物。又，如苯均四酸二醯亞胺般，可為醯亞胺化二羧酸酐之二醯亞胺化合物，或於末端具有醯亞胺基之化合物。從容易得到交聯體的觀點來看，醯亞胺化合物以具有聚合性之不飽和鍵為佳，作為該不飽和醯亞胺化合物可為馬來醯亞胺或具有降莰烯構造之醯亞胺化合物。 As a quinone imine reacted with B, B', B"-trichloroborazine The compound may be exemplified below. Maleic imine, citraconin, ylide, itaconimide, phthalimide, nadic acid imide, nadic acid imide, methyl nadic acid imide, Cis-4-cyclohexene-1,2-dicarboxylic acid quinone imine, cis-1,2-cyclohexanedicarboxylate imine, allyl nadic acid ruthenium imine, etc. Compound. Further, as the pyromellitic acid diimide, it may be a quinone imine compound of a ruthenium dicarboxylic acid anhydride or a compound having a quinone imine group at the terminal. From the viewpoint of easily obtaining a crosslinked body, the quinone imine compound is preferably a polymerizable unsaturated bond, and the unsaturated quinone imine compound may be a maleimide or a decylene structure. Amine compound.
上述醯亞胺化合物可僅使用1種，又，雖可混合2種以上使用，但從溶解性或交聯反應控制的觀點來看時，以僅使用1種為佳。 The above-mentioned quinone imine compound may be used alone or in combination of two or more. However, it is preferred to use only one type from the viewpoint of solubility or control of crosslinking reaction.
作為B,B’,B”-三氯環硼氮烷與醯亞胺化合物 的反應時所使用之溶劑，若為不與原料反應之溶劑雖並無特別限定，但可使用己烷、甲苯、庚烷、苯、二甲苯等之烴溶劑、二氯甲烷、氯仿、四氯化碳等之含氯系溶劑、四氫呋喃、二***等之醚系溶劑等。較佳為甲苯、氯苯。溶劑可推薦經脫水者。此等之溶劑可單獨使用，可適當組合二種以上使用。反應器以預先以經乾燥之惰性氣體取代為 佳。 As B, B', B"-trichloroborazine and quinone compound The solvent used in the reaction is not particularly limited as long as it is a solvent which does not react with the raw material, but a hydrocarbon solvent such as hexane, toluene, heptane, benzene or xylene, dichloromethane, chloroform or tetrachlorobenzene can be used. A chlorine-based solvent such as carbon, an ether solvent such as tetrahydrofuran or diethyl ether, or the like. Preferred is toluene or chlorobenzene. Solvents can be recommended for dehydration. These solvents may be used singly or in combination of two or more kinds as appropriate. The reactor is replaced by a previously dried inert gas good.
反應可藉由將B,B’,B”-三氯環硼氮烷加熱溶解於溶劑後，添加醯亞胺化合物進行。添加後在溶劑之沸點使其回流。又，反應時由於產生氯化氫氣體，有必要在系統外進行對純水之接收器等之廢氣體的處理。 The reaction can be carried out by heating B, B', B"-trichloroborazine in a solvent and adding a quinone compound. After the addition, the solvent is refluxed at the boiling point of the solvent. Further, hydrogen chloride gas is generated during the reaction. It is necessary to carry out the treatment of the exhaust gas body of the pure water receiver or the like outside the system.
反應溫度雖因溶劑等而有所不同，但通常以於0~200℃，較佳於100~150℃下進行為佳。由於反應溫度過高時反應的控制變為困難，過低時反應速度變遲緩故不佳。 Although the reaction temperature varies depending on the solvent, etc., it is usually carried out at 0 to 200 ° C, preferably at 100 to 150 ° C. Since the control of the reaction becomes difficult when the reaction temperature is too high, the reaction rate becomes too slow when it is too low, which is not preferable.
反應時間雖因原料或溶劑等而有所不同，但通常為3~24小時。較佳為3~10小時。 Although the reaction time varies depending on the starting material or solvent, it is usually 3 to 24 hours. It is preferably 3 to 10 hours.
純化步驟以利用溶解度之差異，進行再沉澱為佳。進而有必要純化時，期望進行再結晶化、昇華純化。 The purification step is preferably carried out by re-precipitation using the difference in solubility. Further, when purification is necessary, it is desirable to carry out recrystallization and sublimation purification.
作為本發明之含有醯亞胺基之環硼氮烷的例可列舉以下之構造。惟，並非被限定於此等。 Examples of the quinone group-containing borazine in the present invention include the following structures. However, it is not limited to this.
對於本發明之環硼氮烷交聯體的製造方法之一例說明於以下。惟，並非被限定於此等 An example of a method for producing a borazine-crosslinked body of the present invention will be described below. However, it is not limited to this.
含有二官能性之馬來醯亞胺基之環硼氮烷化合物(b-11)形成二官能性之酚性羥基之雙酚A(c-1)與組成物時，可藉由於150~250℃進行熱硬化，由下式之反應而得到環硼氮烷交聯體(d-1)。此時，可添加三苯基膦作為促進劑。如此進行所得到之環硼氮烷交聯體由於較環硼氮烷化合物，耐水解性等之穩定性、耐熱性、韌性優異故為佳。因此可使用於層合板、層間絕緣膜、密封材料等之電子材料、塗料、接著劑等各種用途。又，與環硼氮烷化合物相同亦可期待低介電性、高熱傳導性。 When the bis-borane compound (b-11) containing a difunctional quinone imine group forms a bifunctional phenolic hydroxyl group of bisphenol A (c-1) and a composition, it can be used as a 150-250 The temperature hardening was carried out at ° C, and a borazine alkane crosslinked body (d-1) was obtained by the reaction of the following formula. At this time, triphenylphosphine may be added as a promoter. The boraxine crosslinked body obtained in this manner is preferably more excellent in stability, heat resistance, and toughness due to hydrolysis resistance and the like than the borazine compound. Therefore, it can be used for various uses such as an electronic material such as a laminate, an interlayer insulating film, and a sealing material, a coating material, and an adhesive. Further, similarly to the borazine compound, low dielectric properties and high thermal conductivity can be expected.
如此進行所得到之環硼氮烷化合物及環硼氮 烷交聯體由於具有醯亞胺基，與以往之環硼氮烷化合物比較，耐水解性等之穩定性或操作性、製膜性等之加工性、耐熱性、難燃性優異，可使用於層合板、層間絕緣膜、密封材料等之電子材料、塗料、接著劑等各種用途。又，與以往之環硼氮烷化合物相同亦可期待低介電性、高熱傳導性。 The borazine compound and the boron boron nitride thus obtained are carried out in this manner. Since the alkyne crosslinked body has a quinone imine group, it is excellent in workability, heat resistance, and flame retardancy, such as stability, workability, film forming property, and the like, as compared with the conventional borazine compound. It is used in various applications such as electronic materials such as laminates, interlayer insulating films, and sealing materials, paints, and adhesives. Further, similar to the conventional borazine compound, low dielectric properties and high thermal conductivity can be expected.
以下雖更詳細說明使用實施例及比較例之本發明之實施形態，但本發明之技術的範圍並非僅限制於下述之形態。尚且，「%」表示重量基準。 Hereinafter, the embodiments of the present invention using the examples and the comparative examples will be described in more detail, but the scope of the technology of the present invention is not limited to the following aspects. Also, "%" indicates the weight basis.
於具備冷卻管、氮氣體導入管之反應容器，邊取代氮，邊加入脫水甲苯100g冷卻至0℃。保持在0℃進行攪拌，將三氯化硼(1.0M甲苯溶液)100mL緩緩加入注射器使其溶解。之後，將經脫水處理之苯胺9.31g極為緩慢加入注射器耗費約3小時滴下。滴下後，慢慢將溫度昇溫 至110℃，氮氣流下，加熱20小時使其回流。將反應液在甲苯再結晶化後，進行昇華純化，調製白色固體之結晶之B,B’,B”-三氯-N,N’,N”-三苯基環硼氮烷(a-3)。收量16.0g、收率90%。 In a reaction vessel equipped with a cooling tube and a nitrogen gas introduction tube, 100 g of dehydrated toluene was added thereto while cooling with nitrogen, and the mixture was cooled to 0 °C. While stirring at 0 ° C, 100 mL of boron trichloride (1.0 M toluene solution) was gradually added to the syringe to dissolve. Thereafter, the dehydrated aniline 9.31 g was added to the syringe very slowly and it took about 3 hours to drip. After dripping, slowly warm the temperature The mixture was heated to 110 ° C under a nitrogen stream for 20 hours to reflux. After the reaction solution was recrystallized in toluene, sublimation purification was carried out to prepare a white solid crystal of B, B', B"-trichloro-N, N', N"-triphenylborazine (a-3). ). The yield was 16.0 g and the yield was 90%.
其次，於具備冷卻管、氮氣體導入管之反應 容器，邊取代氮，邊加入脫水氯苯100g冷卻至0℃。加入B,B’,B”-三氯-N,N’,N”-三苯基環硼氮烷(a-3)5.00g與納迪克酸醯亞胺5.94g後，邊慢慢將溫度昇溫至130℃邊攪拌。氮氣流下，加熱20小時使其回流。確認藉由反應抑制氯化氫氣體之產生後，冷卻至室溫。過濾沉澱物，以脫水甲苯洗淨後，得到B,B’,B”-三氯-N,N’,N”-三苯基環硼氮烷(a-3)之3個氯基當中之1個被納迪克酸醯亞胺基所取代之環硼氮烷化合物、2個為被納迪克酸醯亞胺基所取代之環硼氮烷化合物及3個為被納迪克酸醯亞胺基所取代之環硼氮烷化合物之混合物。昇華純化此混合物，得到上述3個為被納迪克酸醯亞胺基所取代之環硼氮烷化合物，亦即白色固體之含有納迪克酸醯亞胺基之環硼氮烷化合物(a-4)。收量7.2g、收率74.9%。 Secondly, the reaction with a cooling tube and a nitrogen gas introduction tube The vessel was replaced with nitrogen, and 100 g of dehydrated chlorobenzene was added thereto and cooled to 0 °C. After adding B, B', B"-trichloro-N, N', N"-triphenylborazine (a-3) 5.00 g and 5.13 g of nadic acid ylide, slowly set the temperature Stir at a temperature of 130 °C. Under a nitrogen stream, it was heated for 20 hours to reflux. It was confirmed that the generation of hydrogen chloride gas was suppressed by the reaction, and then cooled to room temperature. The precipitate was filtered and washed with dehydrated toluene to obtain three chlorine groups of B, B', B"-trichloro-N, N', N"-triphenylborazine (a-3). a borazine compound substituted by a nadic acid sulfonium imino group, two borazine compounds substituted with a nadic acid sulfonium imide group, and three yttrium nitrite groups A mixture of substituted borazine compounds. Purification of the mixture by sublimation to obtain the above three borazine compounds which are substituted with a nadic acid sulfonium imide group, that is, a white solid borazine compound containing a nadic acid sulfonium imide group (a-4) ). The yield was 7.2 g and the yield was 74.9%.
生成物之同定以1H-NMR、IR測定、元素分析進行，確認為含有納迪克酸醯亞胺基之環硼氮烷化合物。 The product was determined by 1 H-NMR, IR measurement, and elemental analysis, and was confirmed to be a borazine compound containing a nadic acid sulfonium imino group.
摻合上述環硼氮烷化合物(a-4)25.0重量份、環氧樹脂(o-甲酚酚醛清漆型環氧樹脂；OCNE、環氧當量200、軟化點65℃)65.2重量份、交聯劑(酚酚醛清漆樹脂；PN、OH當量107、軟化點80℃)34.8重量份、作為促進劑之三苯基膦1重量份，製作樹脂組成物。進而將此樹脂組成物於175℃進行轉印成型，將後固化在250℃下3小時進行後固化，得到交聯體試驗片之後，進行各種物性測定。 25.0 parts by weight of the above borazine compound (a-4), epoxy resin (o-cresol novolak type epoxy resin; OCNE, epoxy equivalent 200, softening point 65 ° C) 65.2 parts by weight, cross-linking A resin composition was prepared by using 34.8 parts by weight of a phenol novolak resin (PN, OH equivalent 107, softening point 80 ° C) and 1 part by weight of triphenylphosphine as a promoter. Further, this resin composition was subjected to transfer molding at 175 ° C, and post-curing was post-cured at 250 ° C for 3 hours to obtain a crosslinked test piece, and various physical properties were measured.
於具備冷卻管、氮氣體導入管之反應容器，邊取代氮，邊加入脫水氯苯100g冷卻至0℃。加入B,B’,B”-三氯-N,N’,N”-三苯基環硼氮烷(a-3)5.00g與馬來醯亞胺3.54g後，邊慢慢將溫度昇溫至130℃邊攪拌。氮氣流下，加熱20小時使其回流。確認藉由反應抑制氯化氫氣體之產生後，冷卻至室溫。過濾沉澱物，以脫水甲苯洗淨後，得到B,B’,B”-三氯-N,N’,N”-三苯基環硼氮烷(a-3)之3個氯基當中之1個被馬來醯亞胺基所取代之環硼氮烷化合物、2個為被馬來醯亞胺基所取代之環硼氮烷化合物及3個為被馬來醯亞胺基所取代之環硼氮烷化合物之混合物。昇華純化此混合物，得到上述3個為被馬來醯亞胺基所取代之環硼氮烷化合物，亦即白色固體之含有馬來醯亞胺基之環硼氮烷化合物(a-5)。收量5.1g、收率70.8%。 In a reaction vessel equipped with a cooling tube and a nitrogen gas introduction tube, 100 g of dehydrated chlorobenzene was added thereto while cooling with nitrogen, and the mixture was cooled to 0 °C. After adding B, B', B"-trichloro-N, N', N"-triphenylborazine (a-3) 5.00g and 3.54g of maleimide, slowly increase the temperature Stir at 130 °C. Under a nitrogen stream, it was heated for 20 hours to reflux. It was confirmed that the generation of hydrogen chloride gas was suppressed by the reaction, and then cooled to room temperature. The precipitate was filtered and washed with dehydrated toluene to obtain three chlorine groups of B, B', B"-trichloro-N, N', N"-triphenylborazine (a-3). a borazine compound substituted with a maleimine group, two borazine compounds substituted with a maleimine group, and three substituted with a maleimine group a mixture of borazine compounds. The mixture was purified by sublimation to obtain the above three borazine compounds which were substituted with a maleimine group, that is, a maleicimido group-containing borazine compound (a-5) which was a white solid. The yield was 5.1 g and the yield was 70.8%.
生成物之同定係以1H-NMR、IR測定、元素分析進行，確認為含有馬來醯亞胺基之環硼氮烷化合物(a-5)。 The homologue of the product was determined by 1 H-NMR, IR measurement, and elemental analysis, and was confirmed to be a borazine compound (a-5) containing a maleimide group.
又，除了取代環硼氮烷化合物(a-4)，改使 用上述環硼氮烷化合物(a-5)之外，其他與實施例1以同樣條件製造樹脂組成物及交聯體。 Further, in addition to replacing the borazine compound (a-4), A resin composition and a crosslinked body were produced under the same conditions as in Example 1 except that the above borazine compound (a-5) was used.
於具備冷卻管、氮氣體導入管之反應容器，邊取代氮，邊加入脫水氯苯100g冷卻至0℃。加入B,B’,B”-三氯-N,N’,N”-三苯基環硼氮烷(a-3)5.00g與檸康酸醯亞胺4.04g後，邊慢慢將溫度昇溫至130℃邊攪拌。氮氣流下，加熱20小時使其回流。確認藉由反應抑制氯化氫氣體之產生後，冷卻至室溫。過濾沉澱物，以脫水甲苯洗淨後，得到B,B’,B”-三氯-N,N’,N”-三苯基環硼氮烷(a-3)之3個氯基當中之1個被檸康酸醯亞胺基所取代之環硼氮烷化合物、2個為被檸康酸醯亞胺基所取代之環硼氮烷化合物及3個為被檸康酸醯亞胺基所取代之環硼氮烷化合物之混合物。昇華純化此混合物，得到上述3個為被檸康酸醯亞胺基所取代之環硼氮烷化合物，亦即白色固體之含有檸康酸醯亞胺基之環硼氮烷化合物(b-18)。收量6.9g、收率70.5%。 In a reaction vessel equipped with a cooling tube and a nitrogen gas introduction tube, 100 g of dehydrated chlorobenzene was added thereto while cooling with nitrogen, and the mixture was cooled to 0 °C. After adding B, B', B"-trichloro-N, N', N"-triphenylborazine (a-3) 5.00g and 4.04g of citronine citrate, slowly set the temperature Stir at a temperature of 130 °C. Under a nitrogen stream, it was heated for 20 hours to reflux. It was confirmed that the generation of hydrogen chloride gas was suppressed by the reaction, and then cooled to room temperature. The precipitate was filtered and washed with dehydrated toluene to obtain three chlorine groups of B, B', B"-trichloro-N, N', N"-triphenylborazine (a-3). a borazine compound substituted with ruthenium citrate, two borazine compounds substituted with ruthenium citrate, and three ruthenium citrate groups A mixture of substituted borazine compounds. Purification of the mixture by sublimation to obtain the above three borazine compounds which are substituted with ruthenium citrate, which is a white solid borazine compound containing ruthenium citrate (b-18) ). The yield was 6.9 g and the yield was 70.5%.
生成物之同定係以1H-NMR、IR測定、元素分析進行，確認為含有馬來醯亞胺基之環硼氮烷化合物。 The homologue of the product was determined by 1 H-NMR, IR measurement, and elemental analysis, and was confirmed to be a borazine compound containing a maleidino group.
又，除了取代環硼氮烷化合物(a-4)，改使用上述環硼氮烷化合物(b-18)之外，其他與實施例1以同樣條件製造樹脂組成物及交聯體。 Further, a resin composition and a crosslinked product were produced under the same conditions as in Example 1 except that the above borazine compound (b-18) was used instead of the borazine compound (a-4).
於具備冷卻管、氮氣體導入管之反應容器，邊取代氮，邊加入脫水氯苯100g冷卻至0℃。加入B,B’,B”-三氯-N,N’,N”-三苯基環硼氮烷(a-3)5.00g(0.0121mol)與雙環己基胺6.61g(0.0364mol)後，邊慢慢將溫度昇溫至130℃邊攪拌。氮氣流下，加熱20小時使其回流。確認藉由反應抑制氯化氫氣體之產生後，冷卻至室溫。過濾沉澱物，以脫水甲苯洗淨後，得到B,B’,B”-三氯-N,N’,N”-三苯基環硼氮烷(a-3)之3個氯基當中之1個被雙環己基胺基所取代之環硼氮烷化合物、2個為被雙環己基胺基所取代之環硼氮烷化合物及3個為被雙環己基胺基所取代之環硼氮烷化合物之混合物。昇華純化此混合物，上述3個為被雙環己基胺基所取代之環硼氮烷化合物，亦即進行昇華純化得到白色固體之B,B’,B”-三(雙環己基胺基)-N,N’,N”-三苯基環硼氮烷(a-6)。收量9.4g、收率91.5%。 In a reaction vessel equipped with a cooling tube and a nitrogen gas introduction tube, 100 g of dehydrated chlorobenzene was added thereto while cooling with nitrogen, and the mixture was cooled to 0 °C. After adding B, B', B"-trichloro-N, N', N"-triphenylborazine (a-3) 5.00 g (0.0121 mol) and dicyclohexylamine 6.61 g (0.0364 mol), Stir slowly while warming the temperature to 130 °C. Under a nitrogen stream, it was heated for 20 hours to reflux. It was confirmed that the generation of hydrogen chloride gas was suppressed by the reaction, and then cooled to room temperature. The precipitate was filtered and washed with dehydrated toluene to obtain three chlorine groups of B, B', B"-trichloro-N, N', N"-triphenylborazine (a-3). a borazine compound substituted with a dicyclohexylamino group, two borazine compounds substituted with a dicyclohexylamino group, and three borazine compounds substituted with a biscyclohexylamino group. mixture. The mixture is purified by sublimation, and the above three are borazine compounds substituted by a dicyclohexylamine group, that is, sublimed and purified to obtain a white solid B, B', B"-tris(dicyclohexylamino)-N, N',N"-triphenylborazine (a-6). The yield was 9.4 g and the yield was 91.5%.
生成物之同定係以1H-NMR、IR測定、元素分析進行，確認為含有雙環己基胺基之環硼氮烷化合物。 The homologue of the product was determined by 1 H-NMR, IR measurement, and elemental analysis, and was confirmed to be a bisboroylamine group-containing borazine compound.
又，除了取代環硼氮烷化合物(a-4)，改使用上述環硼氮烷化合物(a-6)之外，其他與實施例1以同樣條件製造樹脂組成物及交聯體。 Further, a resin composition and a crosslinked product were produced under the same conditions as in Example 1 except that the above borazine compound (a-6) was used instead of the borazine compound (a-4).
將於實施例1所合成之環硼氮烷化合物(a-4)之中間生成物之B,B’,B”-三氯-N,N’,N”-三苯基環硼氮烷(a-3)作為環硼氮烷化合物(a-3)。 B, B', B"-trichloro-N, N', N"-triphenylborazine (Intermediate product of the borazine compound (a-4) synthesized in Example 1 ( A-3) as a borazine compound (a-3).
又，除了取代環硼氮烷化合物(a-4)，改使用上述環硼氮烷化合物(a-3)之外，其他與實施例1以同樣條件製造樹脂組成物及交聯體。 Further, a resin composition and a crosslinked product were produced under the same conditions as in Example 1 except that the above borazine compound (a-3) was used instead of the borazine compound (a-4).
對於於以上之實施例及比較例所得之環硼氮烷化合物，測定耐熱性、溶解性及其他特性。 Heat resistance, solubility, and other characteristics were measured for the borazine compound obtained in the above Examples and Comparative Examples.
耐熱性評估係使用示差熱熱重量同時測定裝置(裝置名：SII．奈米科技製TG/DTA7300)，以200mL/min之氮氣流、10℃/min之昇溫速度的條件，測定10%重量減少溫度(Td 10)及在900℃之重量減少(殘碳率)。 The heat resistance evaluation was carried out by using a differential thermal and thermal weight simultaneous measuring device (device name: TG/DTA7300 manufactured by SII. Nanotech Co., Ltd.), and measuring a 10% weight loss under the conditions of a nitrogen gas flow rate of 200 mL/min and a temperature increase rate of 10 ° C/min. Temperature (T d 10 ) and weight reduction at 900 ° C (residual carbon ratio).
溶解性之判定係於溶劑(THF及甲苯)1g中投入上述之環硼氮烷化合物50mg，於室溫下充分攪拌後，確認不溶物質。以目視確認，為不溶物質時記為×， 不是時記為○。 In the determination of the solubility, 50 mg of the above borazine compound was added to 1 g of a solvent (THF and toluene), and the mixture was thoroughly stirred at room temperature to confirm an insoluble matter. It is confirmed by visual inspection that it is × when it is insoluble matter. It is not ○ when it is not.
耐水解性評估於包含純水10mg之溶劑中(甲苯)1g投入上述之環硼氮烷化合物50mg，於室溫下充分攪拌後，將水解成分之胺化合物之苯胺在1H-NMR進行分析，將檢出胺化合物時記為×。 Hydrolysis resistance evaluation 50 mg of the above borazine compound was added to 1 g of a solvent containing 10 mg of pure water (toluene), and after sufficiently stirring at room temperature, the aniline of the amine compound of the hydrolyzed component was analyzed by 1 H-NMR. When the amine compound is detected, it is recorded as ×.
透過率係將上述環硼氮烷化合物之甲苯溶液使用紫外可視分光光度計(V-650，日本分光股份有限公司製)測定，於400nm之透過率為80%以上時記為○，未達80%時記為×。 The transmittance of the toluene solution of the above borazine compound was measured using an ultraviolet visible spectrophotometer (V-650, manufactured by JASCO Corporation), and when the transmittance at 400 nm was 80% or more, it was recorded as ○, which was less than 80. When % is recorded as ×.
又，評估環硼氮烷交聯體的特性。 Further, the properties of the borazine alkane crosslinked body were evaluated.
玻璃轉移點(Tg)係將環硼氮烷交聯體使用熱機械測定裝置(TMA/SS7100、SII．奈米科技製)，以200mL/min之氮氣流下、5℃/min之昇溫速度的條件測定。 The glass transition point (Tg) is a condition in which the borazine azide crosslinked body is subjected to a thermomechanical measuring device (TMA/SS7100, manufactured by SII. Nanotechnology Co., Ltd.) at a nitrogen gas flow rate of 200 mL/min and a heating rate of 5 ° C/min. Determination.
介電率係使用介電率測定裝置(N274，AET製)，在同軸共振法以2GHz、25℃之條件測定。 The dielectric constant was measured by a coaxial resonance method at 2 GHz and 25 ° C using a dielectric constant measuring device (N274, manufactured by AET).
樹脂組成物之成型性的判定係在轉印成型機以175℃製作彎曲試驗片時，將可製作未膨潤或未破裂之均勻試驗片的情況記為○，不可製作的情況記為×。 In the case where the bending test piece was produced at 175 ° C in a transfer molding machine, the case where a uniform test piece which was not swollen or not broken was produced was designated as ○, and the case where it could not be produced was designated as ×.
將由此等測定所得到之結果示於表1。 The results obtained by the above measurement are shown in Table 1.
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