CN112442063A - Silane coupling agent with purine ring and imide or amic acid structure, and preparation method and application thereof - Google Patents
Silane coupling agent with purine ring and imide or amic acid structure, and preparation method and application thereof Download PDFInfo
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- CN112442063A CN112442063A CN202011342336.8A CN202011342336A CN112442063A CN 112442063 A CN112442063 A CN 112442063A CN 202011342336 A CN202011342336 A CN 202011342336A CN 112442063 A CN112442063 A CN 112442063A
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- silane coupling
- coupling agent
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 148
- 150000003949 imides Chemical class 0.000 title abstract description 8
- 239000002253 acid Substances 0.000 title abstract description 7
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical group N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 title description 10
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920006015 heat resistant resin Polymers 0.000 claims abstract description 27
- 229920001721 polyimide Polymers 0.000 claims abstract description 26
- 229920002577 polybenzoxazole Polymers 0.000 claims abstract description 20
- 230000001737 promoting effect Effects 0.000 claims abstract description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 47
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 20
- 239000004642 Polyimide Substances 0.000 claims description 16
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 16
- 238000007112 amidation reaction Methods 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 12
- -1 amino, mercapto, carbonyl Chemical group 0.000 claims description 11
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 11
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 150000007514 bases Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 239000003779 heat-resistant material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 239000009719 polyimide resin Substances 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 6
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 6
- ZADOWCXTUZWAKL-UHFFFAOYSA-N 3-(3-trimethoxysilylpropyl)oxolane-2,5-dione Chemical compound CO[Si](OC)(OC)CCCC1CC(=O)OC1=O ZADOWCXTUZWAKL-UHFFFAOYSA-N 0.000 description 5
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 229930024421 Adenine Natural products 0.000 description 3
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229960000643 adenine Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000005447 octyloxy group Chemical group [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])O* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- AXMANIZPMQZKTG-UHFFFAOYSA-N 4-(2-phenylethynyl)-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C2=C1C=CC=C2C#CC1=CC=CC=C1 AXMANIZPMQZKTG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012948 isocyanate Chemical group 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The silane coupling agent has a purine ring and an imide or amic acid structure, and has a remarkable promoting effect on the adhesion of heat-resistant resins such as polyimide resins, polybenzoxazole resins and the like and base materials.
Description
Technical Field
The invention relates to an organic silicon compound, in particular to a silane coupling agent with purine rings and imide or amic acid structures, a preparation method and application thereof.
Background
Polyimide resins, polybenzoxazole resins, and the like, which are excellent in heat resistance, mechanical properties, and the like, have been widely used as surface protective films, interlayer insulating films, and the like of semiconductor elements of electronic devices. The heat-cured film exists as a permanent film in the device, and therefore, the properties of the heat-cured film are very important. Adhesion of the cured film to the surface material of the semiconductor chip is very important in order to ensure reliability of the semiconductor package.
Organosilicon compounds having hydrolyzable silane groups and organic reactive groups are generally referred to as "silane coupling agents", which are capable of "coupling" organic and inorganic materials by chemical bonding therebetween and are therefore frequently used as adhesives, coating additives, and resin modifiers. Typical organic reactive groups are vinyl, amino, mercapto, epoxy, isocyanate, (meth) acryloxy, styryl, and the like. Since the adhesion of a heat-resistant resin to a base material, particularly a metal base material, which is known in the prior art is not sufficient, it has been proposed to improve the adhesion of a heat-resistant resin film to a base material by pretreating the base material with a silane coupling agent or the like, adding a silane coupling agent to a heat-resistant resin precursor composition (hereinafter referred to as a coating paste), or adding an organic silicon compound capable of participating in polymerization during the synthesis of a heat-resistant resin precursor. Among these methods, the method of adding a silane coupling agent to a coating paste is the simplest. Silane coupling agents suitable for use with high heat resistant organic materials such as high molecular weight polymers like polyimides and polybenzoxazoles generally have a structure that undergoes some reaction with or has a chemical structure similar to that of the functional groups in the high molecular weight polymer to promote adhesion of the heat resistant organic material to the substrate.
JP-A2009-015285, JP-A2010-152302 and WO2009/096050 disclose that a silane coupling agent containing an imide structural group has good compatibility with a heat-resistant resin having a polyimide structure and exhibits a good adhesion promoting effect with a substrate. Since the structure of polyimide does not have strong chemical bonding capability, the adhesion between the polymer material and the substrate (especially, the metal substrate) is greatly improved.
Enhanced adhesion of phenylethynyl phthalic anhydride-modified silane coupling agents on metal substrates is described in chemical agents 2009, 31(7), 538-540. The principle is that the imidization temperature of the polyimide precursor is close to the polymerization temperature of the ethynyl, so that the hydrophobic end alkynyl is polymerized under the high-temperature condition, and the hydrophilic end silicon base is well bonded with the substrate, thereby achieving the effect of enhancing the adhesive force. However, phenylethynyl phthalic anhydride is expensive and not suitable for large-scale industrial use.
Disclosure of Invention
The invention aims to provide a silane coupling agent which has an imide or amic acid structure and a purine ring structure, has good compatibility with heat-resistant resin and also has good promotion effect on the adhesion between the heat-resistant resin and a base material, especially a metal base material.
The invention provides silane coupling agents with purine rings and imide or amic acid structures, which have structural formulas shown in general formulas (1) to (4), wherein the silane coupling agent is one of the structures or a combination of two or more of the structures.
Further, in the general formulae (1) to (4), R is1Is a hydrogen atom, C1-C10Alkyl or C1-C10Alkoxy group of (a); r2Is a hydrogen atom, C1-C10Alkyl or C1-C10Alkoxy group of (a); r3Is a hydrogen atom, C1-C10Alkyl or C1-C10Alkoxy group of (a); r4Is amino, mercapto, carbonyl, hydroxyl, ester group or acyl; r5Is N atom or CH; r6Is hydrogen atom, amino group, mercapto group, hydroxyl group or halogen atom.
Further, in the general formulae (1) to (4), R is1,R2,R3May be the same or different.
The invention also provides a preparation method of the silane coupling agent, wherein the preparation method of the silane coupling agent shown in the formula (1) or the formula (2) comprises the following steps: the silane coupling agent represented by the above formula (1) or formula (2) can be obtained by subjecting a compound represented by the following formula (5) or formula (6) and a compound represented by the following formula (7) to an amidation reaction.
The preparation method of the silane coupling agent represented by the formula (3) or the formula (4) comprises the following steps: the silane coupling agent represented by formula (1) or formula (2) is imidized to obtain a silane coupling agent represented by formula (3) or formula (4).
Further, when a plurality of silane coupling agents are selected, the silane coupling agents obtained may be mixed and used.
Further, in the above formula (5) to formula (7), R1、R2、R3、R4、R5、R6The definitions of (a) are consistent with the definitions described above.
It has been verified by experiments that the silane coupling agents having the structures represented by the general formulae (1) to (4) in the present invention are effective for promoting adhesion of heat-resistant resins such as polyimide and its precursor, polybenzoxazole and its precursor to substrates (silicon, ceramics, metals, etc., particularly copper or copper alloys). Based on the excellent performance, the invention also provides the application of the silane coupling agent with the structural formula shown in the general formulas (1) to (4) in promoting the adhesion of the heat-resistant resin and the base material. The heat-resistant resin includes a polyimide-based resin, a polybenzoxazole-based resin, and the like.
Preferably, the polyimide-based resin includes a polyimide resin, a polyamic acid resin, or a polyamic acid ester resin. The polybenzoxazole resin includes hydroxypolyamide resin.
Further, the amount of the silane coupling agent is 0.1 to 20%, more preferably 1 to 10% by mass of the heat-resistant resin. Less than 0.1%, the silane coupling fails to exert a satisfactory adhesion-promoting effect; whereas more than 20% may impair the stability of the resin composition, and when the resin composition is applied to the surface of a substrate, the mechanical properties and heat resistance of the heat-resistant resin film formed are seriously degraded.
The silane coupling agent not only has an imide or amic acid structure similar to polyimide, but also has purine rings, and has a remarkable promoting effect on the adhesion of polyimide and polybenzoxazole polymers to base materials, particularly copper or copper alloys. The silane coupling agent has the advantages of simple preparation process, low cost, suitability for industrial production and good application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a silane coupling agent with a novel structure, which can be a single organic silicon compound or a combination of a plurality of organic silicon compounds, wherein the organic silicon compounds have structural formulas shown in the following general formulas (1) to (4):
in the formulae (1) to (4), R1、R2、R3Each independently may be H atom, C1-C10Alkyl or C1-C10Alkoxy of C1-C10The alkyl group of (b) may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., preferably methyl or ethyl; c1-C10The alkoxy group of (b) may be methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, etc., preferably methoxy or ethoxy. R1、R2、R3May be the same or different. For example R1、R2、R3May be both H atoms and C atoms1-C10Alkyl of (C) at the same time1-C10Or one of them may be a H atom and the other two may be C at the same time1-C10Alkyl or C1-C10Or one of them C1-C10Alkyl of (a) and the other two are simultaneously H atoms or C1-C10Or one of them may be C1-C10Alkoxy of (A) and two of (B) are simultaneously C1-C10Or an alkyl or H atom of, or R1、R2、R3All are different.
Preferably, R1、R2、R3Are each independently C1-C10Alkyl or C1-C10Alkoxy of (i.e. R)1、R2、R3Are all selected from C1-C10Alkyl or C1-C10Alkoxy group of (2). More preferably, R1、R2、R3Are each independently C1-C4Alkyl or C1-C4Alkoxy group of (2). More preferably, R1、R2、R3Each independently is methoxy or ethoxy. R1、R2、R3May be the same or different.
In the formulae (1) and (3), R4Is amino, sulfhydryl, carbonyl, hydroxyl, ester group, acyl, etc.; preferably, R4Is hydroxyl, sulfydryl or carbonyl.
In the formulae (1) to (4), R5Is N atom or CH.
In the formulae (2) and (4), R6Is H atom, amino group, mercapto group, hydroxyl group, halogen atom, etc.
The silane coupling agents of the present invention, formula (1) and formula (3), may be of the following structures: r4Is carbonyl, R5Is a N atom, R1、R2、R3Are both methoxy; r4Is carbonyl, R5Is a N atom, R1、R2、R3Are all ethoxy; r4Is carbonyl, R5Is a N atom, R1、R2、R3Are all pentoxy groups; r4Is carbonyl, R5Is a N atom, R1、R2、R3Are all octoxy groups; r4Is mercapto, R5Is CH, R1、R2、R3Are both methoxy; r4Is mercapto, R5Is CH, R1、R2、R3Are all ethoxy; r4Is mercapto, R5Is CH, R1、R2、R3Are all pentoxy groups; r4Is mercapto, R5Is CH, R1、R2、R3Are all octoxy groups; r4Is mercapto, R5Is CH, R1、R2、R3Are both methoxy; r4Is mercapto, R5Is CH, R1、R2、R3Are all ethoxy; r4Is mercapto, R5Is CH, R1、R2、R3Are all pentoxy groups; r4Is mercapto, R5Is CH, R1、R2、R3Are both octyloxy.
The silane coupling agents of the present invention, formula (2) and formula (4), may be of the following structures: r5Is a N atom, R6Is a H atom, R1、R2、R3Are both methoxy; r5Is a N atom, R6Is a H atom, R1、R2、R3Are all ethoxy; r5Is a N atom, R6Is a H atom, R1、R2、R3Are all pentoxy groups; r5Is a N atom, R6Is a H atom, R1、R2、R3Are all octoxy groups; r5Is CH, R6Is a H atom, R1、R2、R3Are both methoxy; r5Is CH, R6Is a H atom, R1、R2、R3Are all ethoxy; r5Is CH, R6Is a H atom, R1、R2、R3Are all pentoxy groups; r5Is CH, R6Is a H atom, R1、R2、R3Are all octoxy groups; r5Is CH, R6Is a H atom, R1、R2、R3Are both methoxy; r5Is CH, R6Is a H atom, R1、R2、R3Are all ethoxy; r5Is CH, R6Is a H atom, R1、R2、R3Are all pentoxy groups; r5Is CH, R6Is a H atom, R1、R2、R3Are both octyloxy.
Further, the silane coupling agent can preferably promote the adhesion between the heat-resistant resin and the substrate in practical use. From the viewpoint of ease of preparation and cost, the silane coupling agent of the present invention is more preferably: r1、R2、R3Each independently is methoxy or ethoxy, R4Is mercapto or carbonyl, R5Is N atom or CH, R6Is the structure of an H atom.
Further, the silane coupling agent of the present invention is more preferably, from the viewpoint of adhesion effect: r1、R2、R3Each independently is methoxy or ethoxy, R4Is mercapto, R5Is N atom or CH, R6Is the structure of an H atom.
In view of all aspects, the silane coupling agents of the present invention are most preferably of the following structure:
the preparation method of the silane coupling agent comprises the following steps:
1) performing amidation reaction on a compound shown in a general formula (5) or a compound shown in a general formula (6) and a compound shown in a general formula (7) to obtain a silane coupling agent shown in a formula (1) or a formula (2);
2) a silane coupling agent represented by the formula (3) or (4) can be obtained by subjecting a compound represented by the following general formula (5) or a compound represented by the following general formula (6) and a compound represented by the general formula (7) to an amidation reaction and then to an imidization reaction.
In the formulae (5), (6) and (7), R1、R2、R3、R4、R5、R6The definitions of (a) and (b) are all consistent with the foregoing.
Further, in a specific embodiment of the present invention, the compound represented by the formula (7) is: 3- (trimethoxy silane) propyl succinic anhydride, 3- (triethoxy silane) propyl succinic anhydride.
Further, the molar ratio of the compound represented by formula (5) or formula (6) to the compound represented by formula (7) is 1: 0.9-1.1.
Further, the amidation reaction between the compound represented by the formula (5) or (6) and the compound represented by the formula (7) is carried out in an aprotic polar solvent, and the effect of each aprotic polar solvent is equivalent. The aprotic polar solvent can be any solvent with aprotic polar property reported in the prior art, and the compound shown in the formula (5) or the formula (6) and the compound shown in the formula (7) can be subjected to amidation reaction in various aprotic polar solvents. In view of cost and convenience of access, the aprotic polar solvent may be selected from at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and γ -butyrolactone, and dimethylsulfoxide or/and N, N-dimethylacetamide are commonly used.
Further, the aprotic polar solvent serves to provide a reaction environment for the amidation reaction, and the amount thereof may be selected according to the actual circumstances.
Further, the temperature of the amidation reaction may be 0 to 100 ℃ and the reaction may be stopped after the completion of the reaction of the reactants. When the reaction raw material and the solvent are mixed, it is preferable that the compound represented by the formula (5) or (6) and the aprotic polar solvent are mixed at room temperature, and then the compound represented by the formula (7) is added at 0 to 100 ℃. Preferably, the compound of formula (5) or (6) is dissolved in an aprotic polar solvent and then a mixture of the compound of formula (7) and the aprotic polar solvent is added at 0 to 100 ℃.
Further, the method further comprises a step of obtaining the silane coupling agent represented by the formula (1) or (2) by post-treating the reaction solution after the amidation reaction. The post-treatment of the reaction solution includes the steps of removing the solvent and other impurities, and distilling to obtain the product. The solvent can be removed from the reaction solution by rotary evaporation, and impurities, which are mainly unreacted raw materials and by-products formed by the reaction, can be removed by high-temperature reduced-pressure distillation.
Further, the imidization is preferably performed by a chemical imidization method. In the prior art, many chemical imidization has been reported, in which a carboxyl group and an amide group are further imidized by an acid anhydride and a basic compound. The acid anhydride used may be any acid anhydride reported in the art that can be used for imidization, such as acetic anhydride, trifluoroacetic anhydride, and the like, with acetic anhydride being preferred. The basic compound used may be any base reported in the art that can be used for imidization, such as pyridine, triethylamine, diisopropylethylamine, etc., preferably pyridine.
Further, after the amidation reaction to obtain the silane coupling agent represented by the above formula (1) or (2), the reaction solution is directly added with a basic compound and an acid anhydride without extracting the product to further perform imidization reaction, thereby obtaining the silane coupling agent represented by the above formula (3) or (4).
Further, the imidization reaction is also carried out in an aprotic polar solvent, which is in accordance with the definition described above.
Further, the amount of the basic compound to be used is 2 times or more, for example 2 to 10 times, for example, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, or 10 times the molar amount of the compound represented by formula (5) or formula (6). The amount of the acid anhydride to be used is 2 times or more, for example 2 to 10 times, for example, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, or 10 times the molar amount of the compound represented by formula (5) or formula (6).
Preferably, pyridine and acetic anhydride are added to a reaction solution containing the silane coupling agent represented by the formula (1) or the formula (2) to perform chemical imidization. Chemical imidization is carried out at room temperature. The molar amount of pyridine is 2 to 10 times, preferably 2 to 3 times that of the compound represented by formula (5) or formula (6). The molar amount of acetic anhydride is 2 to 10 times, preferably 2 to 3 times that of the compound represented by formula (5) or formula (6).
Further, after the chemical imidization, the method also comprises a step of carrying out post-treatment on the reaction solution to obtain a silane coupling agent product shown in a formula (3) or a formula (4). The post-treatment of the reaction solution includes the steps of removing the solvent and other impurities, and distilling to obtain the product. The solvent can be removed from the reaction solution by rotary evaporation, and impurities, which are mainly unreacted raw materials and by-products formed by the reaction, can be removed by high-temperature reduced-pressure distillation.
The silane coupling agents represented by the general formulae (1) to (4) in the present invention are effective for promoting adhesion of a heat-resistant resin such as a polyimide-based resin or a polybenzoxazole-based resin to a substrate (e.g., silicon, ceramics, or a metal substrate, particularly copper or a copper alloy). Based on the excellent performance, the invention also provides the application of the silane coupling agent with the structural formula shown in the general formulas (1) to (4) in promoting the adhesion of the heat-resistant resin and the base material. The heat-resistant resin includes a polyimide-based resin, a polybenzoxazole-based resin, and the like.
Preferably, the polyimide-based resin includes a polyimide resin, a polyamic acid resin, or a polyamic acid ester resin. The polybenzoxazole resin includes hydroxypolyamide resin.
Tests prove that the performance is better when the dosage of the silane coupling agent is 0.1-20% of the mass of the heat-resistant resin, for example, the dosage can be 0.1%, 0.5%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, and more preferably 1-10% of the mass of the heat-resistant resin. Less than 0.1%, the silane coupling fails to exert a satisfactory adhesion-promoting effect; whereas more than 20% may impair the stability of the resin composition, and when the resin composition is applied to the surface of a substrate, the mechanical properties and heat resistance of the heat-resistant resin film formed are seriously degraded.
The heat treatment of heat-resistant resins such as polyimide-based and polybenzoxazole-based polymers during application causes imidization of the silane coupling agent represented by the general formula (1) or (2) to a different extent, and therefore the silane coupling agent represented by the general formula (1) or (2) is substantially equivalent to the silane coupling agent represented by the general formula (3) or (4) in practical application.
In the following, several embodiments of the present invention are listed to further illustrate the advantages of the present invention, but it should be understood that the following description is only for the purpose of illustrating the present invention and does not limit the contents thereof.
Example 1 (guanine)
Adding 15.1g (0.1mol) of guanine into a 500mL three-necked flask provided with a stirrer and a thermometer, adding 250mL of dimethyl sulfoxide serving as a solvent, putting the three-necked flask into water at 50 ℃, starting stirring, slowly adding 26.2g (0.1mol, X-12-967C, shin-Etsu chemical) of 3- (trimethoxysilyl) propyl succinic anhydride after the guanine is fully dissolved, continuing to react for 2 hours at the temperature after the addition is finished, and performing reduced pressure distillation and purification after the reaction is finished to obtain a silane coupling agent A-1; or cooling the reaction to room temperature, adding 15.8g (0.2mol) of pyridine into the reaction system, stirring uniformly, slowly adding 20.4g (0.2mol) of acetic anhydride, reacting at room temperature for 20hr, after the reaction is finished, distilling under reduced pressure, and removing the solvent, the acetic anhydride, the generated acetic acid and the pyridine in the system to obtain the purified silane coupling agent B-1.
The structural formulas of the obtained silane coupling agents A-1 and B-1 are shown as the following formulas (A-1) and (B-1), wherein R1Is methoxy, R2Is methoxy, R3Is methoxy, R4Is carbonyl, R5Is CH.
The nuclear magnetic information of the silane coupling agent A-1 is as follows:
1HNMR(DMSO):δ:0.56(m,2H),1.23(m,2H),1.49(m,2H),2.0(s,1H),2.56(d,1H),2.66(t,1H),2.81(d,1H),3.55(s,9H),8.35(s,1H),12.09(s,1H),12.21(s,1H),12.80(s,1H)。
the nuclear magnetic information of the silane coupling agent B-1 is as follows:
1HNMR(DMSO):δ:0.56(m,2H),1.23(m,2H),1.49(m,2H),2.62(d,1H),2.87(d,1H),3.55(s,9H),3.59(t,1H),8.35(s,1H),12.09(s,1H),12.80(s,1H)。
example 2 (adenine)
Adding 13.5g (0.1mol) of adenine into a 500mL three-necked flask provided with a stirrer and a thermometer, adding 250mL of dimethyl sulfoxide serving as a solvent, putting the three-necked flask into water at 50 ℃, starting stirring, slowly adding 26.2g (0.1mol, X-12-967C, shin-Etsu chemical) of 3- (trimethoxysilyl) propyl succinic anhydride after the adenine is fully dissolved, continuing to react for 2 hours at the temperature after the addition is finished, and performing reduced pressure distillation and purification after the reaction is finished to obtain a silane coupling agent A-2; or cooling the reaction to room temperature, adding 15.8g (0.2mol) of pyridine into the reaction system, stirring uniformly, slowly adding 20.4g (0.2mol) of acetic anhydride, reacting at room temperature for 20hr, after the reaction is finished, distilling under reduced pressure, and removing the solvent, the acetic anhydride, the generated acetic acid and the pyridine in the system to obtain the purified silane coupling agent B-2.
The structural formulas of the obtained silane coupling agents A-2 and B-2 are shown as the following formulas (A-2) and (B-2), wherein R1Is methoxy, R2Is methoxy, R3Is methoxy, R5Is CH, R6Is an H atom.
The nuclear magnetic information of the silane coupling agent A-2 is as follows:
1HNMR(DMSO):δ：0.56(m,2H),1.23(m,2H),1.49(m,2H),2.56(d,1H),2.66(t,1H),2.81(d,1H),3.55(s,9H),8.35(s,1H),8.60(s,1H),11.21(s,1H),12.21(s,1H),12.80(m,1H)。
the nuclear magnetic information of the silane coupling agent B-2 is as follows:
1HNMR(DMSO):δ：0.56(m,2H),1.23(m,2H),1.49(m,2H),2.62(t,1H),2.87(d,1H),3.55(s,9H),3.59(d,1H),8.35(s,1H),8.60(s,1H),12.80(s,1H)。
example 3 (8-N-guanine)
Adding 15.2g (0.1mol) of 8-N-guanine into a 500mL three-necked flask provided with a stirrer and a thermometer, adding 250mL of dimethyl sulfoxide serving as a solvent, putting the three-necked flask into water at 50 ℃, starting stirring, slowly adding 26.2g (0.1mol, X-12-967C, shin-Etsu chemical) of 3- (trimethoxysilyl) propylsuccinic anhydride after the 8-N-guanine is fully dissolved, continuing to react at the temperature for 2hr after the addition is finished, and performing reduced pressure distillation and purification after the reaction is finished to obtain a silane coupling agent A-3; or cooling the reaction to room temperature, adding 15.8g (0.2mol) of pyridine into the reaction system, stirring uniformly, slowly adding 20.4g (0.2mol) of acetic anhydride, reacting at room temperature for 20hr, after the reaction is finished, distilling under reduced pressure, and removing the solvent, the acetic anhydride, the generated acetic acid and the pyridine in the system to obtain the purified silane coupling agent B-3.
The structural formulas of the obtained silane coupling agents A-3 and B-3 are shown as the following formulas (A-3) and (B-3), wherein R1Is methoxy, R2Is methoxy, R3Is methoxy, R4Is carbonyl, R5Is an N atom.
The nuclear magnetic information of the silane coupling agent A-3 is as follows:
1HNMR(DMSO):δ：0.56(m,2H),1.23(m,2H),1.49(m,2H),2.0(m,1H),2.56(d,1H),2.66(t,1H),2.81(d,1H),3.55(s,9H),10.25(s,1H),12.0(s,1H),12.21(s,1H)。
the nuclear magnetic information of the silane coupling agent B-3 is as follows:
1HNMR(DMSO):δ：0.56(m,2H),1.23(m,2H),1.49(m,2H),2.62(t,1H),2.87(t,1H),3.55(s,9H),3.59(t,1H),10.25(s,1H),12.0(s,1H)。
example 4 (8-N-Heteroadenine)
Adding 13.6g (0.1mol) of 8-N-heteroadenine into a 500mL three-necked flask provided with a stirrer and a thermometer, adding 250mL of dimethyl sulfoxide as a solvent, putting the three-necked flask into a 50 ℃ water solution, starting stirring, slowly adding 26.2g (0.1mol, X-12-967C, shin-Etsu chemical) of 3- (trimethoxysilyl) propylsuccinic anhydride after the 8-N-heteroadenine is fully dissolved, continuing to react at the temperature for 2 hours after the addition is finished, and carrying out reduced pressure distillation and purification after the reaction is finished to obtain a silane coupling agent A-4; or cooling the reaction to room temperature, adding 15.8g (0.2mol) of pyridine into the reaction system, stirring uniformly, slowly adding 20.4g (0.2mol) of acetic anhydride, reacting at room temperature for 20hr, after the reaction is finished, distilling under reduced pressure, and removing the solvent, the acetic anhydride, the generated acetic acid and the pyridine in the system to obtain the purified silane coupling agent B-4.
The structural formulas of the obtained silane coupling agents A-4 and B-4 are shown as the following formulas (A-4) and (B-4), wherein R1Is methoxy, R2Is methoxy, R3Is methoxy, R5Is a N atom, R6Is an H atom.
The nuclear magnetic information of the silane coupling agent A-4 is as follows:
1HNMR(DMSO):δ：0.56(m,2H),1.23(m,2H),1.49(m,2H),2.62(d,1H),2.63(t,1H),2.87(d,1H),3.55(s,9H),8.71(s,1H),11.21(s,1H),12.0(s,1H),12.21(s,1H)。
the nuclear magnetic information of the silane coupling agent B-4 is as follows:
1HNMR(DMSO):0.56(m,2H),1.23(m,2H),1.49(m,2H),2.62(d,1H),2.63(t,1H),2.87(d,1H),3.55(s,9H),8.71(s,1H),12.0(s,1H)。
example 5 (2-amino-6-mercaptoguanine)
Adding 16.7g (0.1mol) of 2-amino-6-mercaptoguanine into a 500mL three-neck flask provided with a stirrer and a thermometer, adding 250mL of dimethyl sulfoxide serving as a solvent, placing the three-neck flask into water at 50 ℃, starting stirring, slowly adding 26.2g (0.1mol, X-12-967C, shiner chemical) of 3- (trimethoxysilyl) propylsuccinic anhydride after the 2-amino-6-mercaptoguanine is fully dissolved, continuing to react for 2hr at the temperature after the addition is finished, and carrying out reduced pressure distillation and purification after the reaction is finished to obtain a silane coupling agent A-5; or cooling the reaction to room temperature, adding 15.8g (0.2mol) of pyridine into the reaction system, stirring uniformly, slowly adding 20.4g (0.2mol) of acetic anhydride, reacting at room temperature for 20hr, after the reaction is finished, distilling under reduced pressure, and removing the solvent, the acetic anhydride, the generated acetic acid and the pyridine in the system to obtain the purified silane coupling agent B-5.
The structural formulas of the obtained silane coupling agents A-5 and B-5 are shown as the following formulas (A-5) and (B-5), wherein R1Is methoxy, R2Is methoxy, R3Is methoxy, R4Is mercapto, R5Is CH.
The nuclear magnetic information of the silane coupling agent A-5 is as follows:
1HNMR(DMSO):δ：0.56(t,2H),1.23(m,2H),1.49(m,2H),2.56(d,1H),2.66(t,1H),2.81(d,1H),3.55(s,9H),8.50(s,1H),11.0(s,1H),12.21(s,1H),12.80(s,1H),13.86(s,1H)。
the nuclear magnetic information of the silane coupling agent B-5 is as follows:
1HNMR(DMSO):δ：0.56(t,2H),1.23(m,2H),1.49(m,2H),2.62(d,1H),2.63(t,1H),2.87(d,1H),3.55(s,9H),8.50(s,1H),12.80(s,1H),13.86(s,1H)。
preparation of resin composition
Reference example 1
Synthesis of polyimide resin
In a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 31.02g (0.1mol) of 4,4' -oxydiphthalic anhydride (ODPA), 100g of N-methylpyrrolidone, 14.80g (0.2mol) of N-butanol and 0.07g (0.0007mol) of triethylamine were sequentially added under a nitrogen stream, and they were stirred and mixed at room temperature to prepare a solution, which was heated to 65 ℃ for 4 hours. Cooling the system to 0-5 deg.C, slowly adding thionyl chloride 23.79g (0.2mol), heating to room temperature after adding thionyl chloride, and reacting for 2hr to obtain acyl chloride solution.
Under nitrogen flow, 36.63g (0.1mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 27.68g (0.35mol) of pyridine and 120mL of N-methylpyrrolidone were sequentially added to another 500mL three-necked flask, and the mixture was uniformly dissolved by stirring at room temperature, cooled to 0 to 5 ℃ and then dropped into the above-prepared acid chloride solution. After the addition, the temperature was raised to room temperature, and the reaction was continued for 4 hr. After the reaction was completed, the reaction solution was poured into 3L of deionized water to precipitate a polymer and obtain a white precipitate. Filtering, washing with deionized water for three times, placing into a vacuum oven, and drying at 80 deg.C for 72hr to obtain polymer, i.e. polyimide resin C-1.
The molecular weight of the polyimide resin C-1 was measured by gel permeation chromatography (GPC, Shimadzu LC-20AD) in terms of standard polystyrene, and the eluent was N-methylpyrrolidone, and the column oven temperature was 40 ℃.
The polyimide resin C-1 has a weight average molecular weight (Mw) of 2.5 to 2.8 ten thousand, a number average molecular weight (Mn) of 1.4 to 1.5 ten thousand, and a molecular weight distribution of 1.6 to 1.7.
20.00g of the polyimide resin C-1 and 30.00g of a gamma-butyrolactone (GBL) solvent were put into a 250ml three-necked flask, stirred, and after the polyimide resin C-1 was completely dissolved, 1.00g of the silane coupling agent A-1 obtained in example 1 was sufficiently dissolved and then filtered through a 1 μm filter to obtain a resin composition having a viscosity of 1400-1500cp as measured at 25 ℃ by a cone and plate viscometer (BROOKFIELD DV2T RV).
Reference example 2
The procedure was repeated as in reference example 1 except that the silane coupling agent A-1 was changed to the silane coupling agent A-2.
Reference example 3
The procedure was repeated as in reference example 1 except that the silane coupling agent A-1 was changed to the silane coupling agent A-3.
Reference example 4
The procedure was repeated as in reference example 1 except that the silane coupling agent A-1 was changed to silane coupling agent A-4.
Reference example 5
The procedure was repeated as in reference example 1 except that the silane coupling agent A-1 was changed to silane coupling agent A-5.
Reference example 6
The procedure was repeated as in reference example 1 except that the silane coupling agent A-1 was changed to silane coupling agent B-1.
Reference example 7
The procedure was repeated as in reference example 1 except that the silane coupling agent A-1 was changed to the silane coupling agent B-2.
Reference example 8
The procedure was repeated as in reference example 1 except that the silane coupling agent A-1 was changed to silane coupling agent B-3.
Reference example 9
The procedure was repeated as in reference example 1 except that the silane coupling agent A-1 was changed to silane coupling agent B-4.
Reference example 10
The procedure was repeated as in reference example 1 except that the silane coupling agent A-1 was changed to silane coupling agent B-5.
Reference example 11
Synthesis of polybenzoxazole resin
32.96g (0.09mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 2.18g (0.02mol) of 4-aminophenol, 15.82g (0.2mol) of pyridine and 100g of N-methylpyrrolidone (NMP) were charged in this order into a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen stream, and after sufficiently dissolving, the temperature of the solution was cooled to-15 ℃. A solution of 29.51g (0.10mol) of 4, 4-diphenyletherdiformylchloride dissolved in 50g of NMP was added dropwise to the flask via a dropping funnel, and the temperature of the reaction mass was controlled to be below 0 ℃ during the addition. After the dropwise addition is finished, the mixture is continuously stirred and reacts for 6 hours at the temperature of between 10 ℃ below zero and 15 ℃ below zero. After the reaction, the reaction mixture was poured into 3L of a 10 wt% aqueous methanol solution to precipitate a polymer, thereby obtaining a white precipitate. Filtering, washing with deionized water for three times, placing in a vacuum oven, and drying at 50 deg.C for 72hr to obtain polymer, i.e. polybenzoxazole resin C-2.
The molecular weight of polybenzoxazole resin C-2 was measured by gel permeation chromatography (GPC, Shimadzu LC-20AD) in terms of standard polystyrene, and the eluent was N-methylpyrrolidone, and the column oven temperature was 40 ℃.
The polybenzoxazole resin C-2 has a weight average molecular weight (Mw) of 2.1 to 2.5 ten thousand, a number average molecular weight (Mn) of 1.3 to 1.6 ten thousand and a molecular weight distribution of 1.3 to 1.5.
20.00g of the polybenzoxazole resin C-2 and 30.00g of a gamma-butyrolactone (GBL) solvent were put into a 250ml three-necked flask, stirred, and after the polybenzoxazole resin C-2 was completely dissolved, 1.00g of the silane coupling agent A-1 obtained in example 1 was added, and after the solution was sufficiently dissolved, the solution was filtered through a 1 μm filter to obtain a resin composition having a viscosity of 1400-1500cp as measured at 25 ℃ by a cone and plate viscometer (BROOKFIELD IEDV 2T RV).
Reference example 12
The procedure was repeated as in reference example 11 except that the silane coupling agent A-1 was changed to silane coupling agent A-2.
Reference example 13
The procedure was repeated as in reference example 11 except that the silane coupling agent A-1 was changed to silane coupling agent A-3.
Reference example 14
The procedure was repeated as in reference example 11 except that the silane coupling agent A-1 was changed to silane coupling agent A-4.
Reference example 15
The procedure was repeated as in reference example 11 except that the silane coupling agent A-1 was changed to silane coupling agent A-5.
Reference example 16
The procedure was repeated as in reference example 11 except that the silane coupling agent A-1 was changed to silane coupling agent B-1.
Reference example 17
The procedure was repeated as in reference example 11 except that the silane coupling agent A-1 was changed to silane coupling agent B-2.
Reference example 18
The procedure was repeated as in reference example 11 except that the silane coupling agent A-1 was changed to silane coupling agent B-3.
Reference example 19
The procedure was repeated as in reference example 11 except that the silane coupling agent A-1 was changed to silane coupling agent B-4.
Reference example 20
The procedure was repeated as in reference example 11 except that the silane coupling agent A-1 was changed to silane coupling agent B-5.
Reference example 21
The same as in reference example 1, except that the amount of the silane coupling agent A-1 was changed from 1.00g to 0.02 g.
Reference example 22
The same as in reference example 1, except that the amount of the silane coupling agent A-1 was changed from 1.00g to 0.20 g.
Reference example 23
The same as in reference example 1, except that the amount of the silane coupling agent A-1 was changed from 1.00g to 2.00 g.
Reference example 24
The same as in reference example 1, except that the amount of the silane coupling agent A-1 was changed from 1.00g to 4.00 g.
Comparative example 1
The procedure was repeated as in reference example 1, except that 1.00g of the silane coupling agent A-1 was changed to 1.00g of the silane coupling agent A-1160 (Beacon chemistry). Wherein A-1160 has the following structural formula:
comparative example 2
The same as in reference example 11, except that 1.00g of the silane coupling agent A-1 was changed to 1.00g of the silane coupling agent A-1160.
Comparative example 3
The procedure of referential example 1 was repeated, except that 1.00g of the silane coupling agent A-1 was changed to 0.66g of the silane coupling agent X-12-967C (shin-Etsu chemical) and 0.34g of 8-N-heteroadenine.
Comparative example 4
The same as in referential example 11 except that 1.00g of the silane coupling agent A-1 was changed to 0.66g of the silane coupling agent X-12-967C (Beacon chemical) and 0.34g of 8-N-heteroadenine.
Comparative example 5
The procedure of referential example 1 was repeated, except that no silane coupling agent was added.
Evaluation tests of resin composition samples were carried out according to the following methods:
each resin composition sample was coated on a 4-inch silicon wafer, followed by soft-baking at 120 ℃ for 3 minutes using a heating stage, and then, the prepared resin cured film was placed in an inert gas oven and heat-treated under a nitrogen stream (oxygen content less than 20 ppm). Firstly, heat treatment is carried out at 170 ℃ for 30 minutes, then the temperature is raised to 320 ℃ for 1 hour, and the curing film is obtained after the treatment at 320 ℃ for 1 hour, and a thickness test of the film is carried out by utilizing a step profiler (KLA Tencor P-7), and the thickness of the film is controlled to be 5 um.
The cured film was scribed into 10 lines by 10 columns of squares using a scriber (model, BYK-Gardner A-5125), peel tests were carried out with tape (special transparent 3M tape) in accordance with the national standard GB/T9286-1998 paint and varnish paint film scribing tests, and the number of the peeled squares was recorded as the peel before PCT.
The cured film was scribed into 10 lines by 10 columns of squares by a scriber (model number, BYK-Gardner A-5125) in the same manner as above, the cured film on which the squares were scribed was subjected to a PCT test (121 ℃ C., 2 atm saturated steam; Dongguan Hong science PCT-30) for 100 hours, and after the PCT test was completed, a peel test was carried out by an adhesive tape in the same manner as above to record the number of squares peeled off as the peeling after PCT.
When the number of peels in the adhesion peel test is less than 10, the adhesion is considered to be good, and when the number is 10 or more, the adhesion is considered to be poor.
The adhesion of the cured film samples prepared above to the substrate was tested according to the adhesion peel test method described previously and the results are shown in table 1 below:
TABLE 1
As can be seen from the above reference examples 1-20, the silane coupling agent of the present invention has a good effect of improving the adhesion between polyimide and polybenzoxazole resins and a substrate, and shows a high adhesion to the substrate even after PCT treatment. The silane coupling agents A-5 and B-5 are most effective in improving the adhesion between the resin and the substrate.
In the range of the amount of the silane coupling agent used being 0.1 to 20% by mass of the heat-resistant resin, the adhesion performance tends to increase and decrease with the increase of the silane coupling agent, and the adhesion decreases with the use of the silane coupling agent exceeding 10%, so that the amount of the silane coupling agent used is preferably 1 to 10% by mass of the heat-resistant resin.
From comparative examples 1-2, although silane coupling agents of different structures all have the effect of improving the adhesion between the resin and the substrate, the improvement effect is significantly lower than that of the present invention.
From comparative examples 3 to 4, it can be seen that the physical mixture of the silane coupling agents X-12-967C and 8-N-heteroadenine, although it also has the effect of improving the adhesion between the resin and the substrate, the improvement effect is significantly lower than that of the present invention.
The alkane coupling agent of the present invention has a significant effect of promoting adhesion between a heat-resistant resin such as a polyimide-based resin or a polybenzoxazole-based resin and a base material, and can significantly improve adhesion of the heat-resistant resin to the base material (silicon, ceramics, metal, etc., particularly copper or a copper alloy). The silane coupling agent can be applied to surface protective films, interlayer insulating layers, secondary wiring insulating layers, flip chip device protective films, protective films with bump structures of flip chip devices, interlayer insulating layers of multi-layer loops, flexible copper clad laminate insulating layers, solder-resistant tin films, liquid crystal orientation agents and the like of semiconductor devices.
Claims (10)
1. A silane coupling agent is characterized in that: the silane coupling agent has structural formulas shown in the following formulas (1) to (4), and the silane coupling agent is one or more of the following structural formulas;
wherein R is1Is a hydrogen atom, C1-C10Alkyl or C1-C10Alkoxy group of (a); r2Is a hydrogen atom, C1-C10Alkyl or C1-C10Alkoxy group of (a); r3Is a hydrogen atom, C1-C10Alkyl or C1-C10Alkoxy group of (a); r4Is amino, mercapto, carbonyl, hydroxyl, ester group or acyl; r5Is N atom or CH; r6Is hydrogen atom, amino group, mercapto group, hydroxyl group or halogen atom.
2. The silane coupling agent according to claim 1, characterized in that: r1、R2、R3Are each independently C1-C4Alkyl or C1-C4Alkoxy group of (a); preferably, R1、R2、R3Each independently is methoxy or ethoxy.
3. The silane coupling agent according to claim 1, characterized in that: r4Is mercapto or carbonyl.
4. The silane coupling agent according to claim 1, characterized in that: r5Is N atom or CH.
5. The silane coupling agent according to claim 1, characterized in that: r6Is a hydrogen atom.
6. The silane coupling agent according to claim 1, characterized in that: which has any one or more of the following structural formulae:
7. a method for producing the silane coupling agent according to claim 1, characterized by comprising the steps of:
carrying out amidation reaction on a compound shown in a formula (5) or a formula (6) and a compound shown in a formula (7) to obtain a silane coupling agent shown in the formula (1) or the formula (2); or, the silane coupling agent represented by formula (1) or formula (2) undergoes imidization to obtain a silane coupling agent represented by formula (3) or formula (4);
in the formulae (5) to (7), R1、R2、R3、R4、R5、R6Is as defined in any one of claims 1 to 5; preferably, the molar ratio of the compound represented by formula (5) or formula (6) to the compound represented by formula (7) is 1: 0.9-1.1.
8. The method of claim 7, wherein: the amidation reaction and the imidization reaction are carried out in an aprotic polar solvent; preferably, the aprotic polar solvent is selected fromN-methyl pyrrolidone,N,N-dimethylformamide,N, N-dimethylacetamide, bisAt least one of methyl sulfoxide and gamma-butyrolactone, preferably dimethyl sulfoxide orN,N-dimethylacetamide.
9. The method of claim 7, wherein: the temperature of amidation reaction is 0-100 ℃;
preferably, the silane coupling agent represented by formula (1) or formula (2) and an acid anhydride are imidized in the presence of a basic compound; preferably, the basic compound is pyridine, triethylamine or diisopropylethylamine, and the anhydride is acetic anhydride or trifluoroacetic anhydride;
preferably, the amount of the basic compound to be used is 2 to 10 times the molar amount of the compound represented by formula (5) or formula (6), and the amount of the acid anhydride to be used is 2 to 10 times the molar amount of the compound represented by formula (5) or formula (6).
10. Use of the silane coupling agent as defined in any one of claims 1 to 6 for promoting adhesion of a heat-resistant material to a substrate; preferably, the heat-resistant resin is a polyimide-based resin or a polybenzoxazole-based resin; preferably, the substrate is silicon, ceramic or metal; preferably, the amount of the silane coupling agent is 0.1 to 20% by mass, more preferably 1 to 10% by mass, of the heat-resistant resin.
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| CN116813660A (en) * | 2023-08-31 | 2023-09-29 | 深圳先进电子材料国际创新研究院 | Tetrazolyl silane coupling agent, preparation method thereof, photosensitive resin composition, preparation method thereof and application thereof |
| CN117234033A (en) * | 2023-08-09 | 2023-12-15 | 波米科技有限公司 | Positive photosensitive resin composition and preparation method and application thereof |
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| CN117234033B (en) * | 2023-08-09 | 2024-04-02 | 波米科技有限公司 | Positive photosensitive resin composition and preparation method and application thereof |
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