CN118719509B - A Parylene coating and its preparation method and application - Google Patents
A Parylene coating and its preparation method and application Download PDFInfo
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- CN118719509B CN118719509B CN202411217163.5A CN202411217163A CN118719509B CN 118719509 B CN118719509 B CN 118719509B CN 202411217163 A CN202411217163 A CN 202411217163A CN 118719509 B CN118719509 B CN 118719509B
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- coupling agent
- parylene
- parylene coating
- substrate
- plated
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- 229920000052 poly(p-xylylene) Polymers 0.000 title claims abstract description 148
- 238000000576 coating method Methods 0.000 title claims abstract description 66
- 239000011248 coating agent Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 154
- 239000000758 substrate Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims description 44
- 238000000151 deposition Methods 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical group NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 5
- 238000000889 atomisation Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 claims description 4
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 4
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 29
- 230000001070 adhesive effect Effects 0.000 abstract description 29
- 238000012545 processing Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 230000009286 beneficial effect Effects 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003814 drug Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- DVYVMJLSUSGYMH-UHFFFAOYSA-N n-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CNCCC[Si](OC)(OC)OC DVYVMJLSUSGYMH-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- NFTVTXIQFYRSHF-UHFFFAOYSA-N 1-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)C(C)OC(=O)C=C NFTVTXIQFYRSHF-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 2
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 acrylic ester Chemical class 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 description 1
- QISNULGCGWEUKY-UHFFFAOYSA-N n-ethyl-2-methylidenebutanamide Chemical compound CCNC(=O)C(=C)CC QISNULGCGWEUKY-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical group CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
Classifications
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- 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
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/102—Pretreatment of metallic substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/104—Pretreatment of other substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
- B05D2203/35—Glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
Abstract
The invention belongs to the technical field of coating materials, and particularly relates to a Parylene coating, a preparation method and application thereof, wherein a coupling agent is arranged between the Parylene layer and a substrate to be plated, the coupling agent has the following general formula of A-M-B, and the mass content of N in the coupling agent is 3% -25%. The invention can improve the adhesive force or the binding force of the Parylene layer on the substrate to be plated, greatly shortens the processing time for achieving high adhesive force, and gives consideration to improving the humidity and heat aging resistance of the Parylene coating.
Description
Technical Field
The invention belongs to the technical field of coating materials, and particularly relates to a Parylene coating, a preparation method and application thereof.
Background
The Parylene layer (Parylene, also called as Parylene) provides various properties such as protective property, lubricating property, barrier property and insulating pressure resistance, and is a novel coating of special materials. The Parylene deposition is a vapor deposition process, and the Parylene itself has extremely strong water vapor barrier efficiency. Since the Parylene material itself is symmetrical (has weak polarity), the adhesive force generated during the process of converting from the gas state to the solid state is just like the liquid state wax to the solid state wax, and the adhesive force can be a little, but the adhesive strength is difficult to be used for industrialization. Thus, the first way of acting on the substrate end is to introduce a very strong polar group, such as carboxyl, phosphate, etc., at the other end of the double bond of the Parylene. The benefit of such groups is that during the phase transition, the polarity of the Parylene is easily changed greatly, thereby creating an electrostatic adsorption effect.
And the second mode of action of the substrate end is that when the surface roughness of the substrate end material is larger, the coupling agent with smaller molecular weight can permeate into the pore canal of the substrate, so as to form a riveted structure (the bonding mode can be understood as a physical mode in a more sense). The potential condition of the bonding mode is that the molecular weight must be matched with that of the pore canal, so that any substance capable of controlling the molecular weight can change the bonding quality (the bonding can be developed in a good direction or a poor direction) in the system. Therefore, generally, either coupling agents of different molecular weights are used to adapt the substrate. Either by sandblasting or by a chemical etching process, the substrate is fitted with a partner agent.
The third mode of interaction with the substrate end is the functional group of the coupling agent itself, which is capable of interacting with the functional group of the substrate surface. The most typical case is that trimethoxysilane can form covalent bonds with hydroxyl groups on the surface of metal oxide ceramic, and finally extremely strong adhesion is achieved.
However, the coupling agent used in the prior art is a silane coupling agent, so that the binding force between the Parylene layer and the substrate to be plated is weak, the adhesion is easy to fall off, and the performance of the Parylene of the substrate to be plated is affected.
In addition, the conventional silane coupling agent is used in the industry, and is mainly prepared by soaking and evaporating, discharging is performed after soaking and evaporating, the adhesive force after discharging can not be immediately improved generally, and the bonding force can be ensured to meet the industrial requirement only through a curing process. That is, the existing silane coupling agent has long process time for improving the adhesive force.
It should be noted that this section of the disclosure only provides a background related to the present disclosure, and does not necessarily constitute prior art or known technology.
Disclosure of Invention
The invention aims to overcome the defects of weak bonding force between a Parylene layer and a substrate to be plated and long process time for improving the adhesive force in the prior art, and provides a Parylene coating, a preparation method and application thereof.
In order to achieve the aim, the invention provides a Parylene coating, which comprises a Parylene layer, wherein a coupling agent exists between the Parylene layer and a substrate to be plated, the coupling agent has the following general formula of A-M-B, and the mass content of N in the coupling agent is 3% -25%.
In some preferred embodiments of the invention, A is selected from H 2C=C(R1) -COO-or H 2C=CH-R2-,R1 is selected from H or alkyl of 1-3 carbon atoms, and R 2 is selected from H, alkyl of 1-10 carbon atoms or phenyl;
B comprises NH 2-、NR3R4-、NHR5-、NH2-(NH)s -CO-, thiourea groups or Wherein the wavy line indicates a bond to M;
Wherein R 3 is selected from alkyl, alkenyl or phenyl with 1-9 carbon atoms, R 4 is selected from alkyl, alkenyl or phenyl with 1-9 carbon atoms, R 3 and R 4 cannot be phenyl at the same time, R 5 is selected from one of alkyl, alkenyl or phenyl with 1-9 carbon atoms, and s is 0-2;
M comprises- (CH 2)n1-、-CO-、-[O-(CH2)n2-O]n3 -), At least one of the groups of (a) is,
Wherein n1 is 0-12, n2 is 1-5, n3 is 1-6;a, b is 1-3, c is 0-3, d is 0-8.
In some preferred embodiments of the invention, A is selected from、、Or (b)Wherein the wavy line indicates a bond with M.
In some preferred embodiments of the invention, B comprises、、、Or (b)Wherein the wavy line indicates a bond with M.
Further preferably, B comprisesOr (b)Wherein the wavy line indicates a bond with M.
In some preferred embodiments of the present invention, the coupling agent is allylamine, acrylamide, diallylamine, triallylamine, N-methylallylamine, N' -diethylacrylamide, 4-acryloylmorpholine, N-dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, 2-acrylic acid hydrazide or。
In some preferred embodiments of the invention, the coupling agent is 0.5% to 7%, preferably 0.5% to 5%, more preferably 0.5% to 3.5% of the mass of the Parylene layer.
In a second aspect, the invention provides a preparation method of a Parylene coating, which is used for the Parylene coating in the first aspect, and the preparation method of the Parylene coating comprises the steps of immersing a substrate to be plated in an organic solution containing a coupling agent, drying, and depositing a Parylene layer.
In some preferred embodiments of the present invention, the coupling agent-containing organic solution is obtained by dissolving the coupling agent in an organic solvent, and the mass concentration of the coupling agent in the coupling agent-containing organic solution is 0.5wt% to 5wt%.
In a second aspect, in some preferred embodiments of the present invention, the soaking time is 1-2 hours, the drying conditions include a drying temperature of 40-80 ℃ for 1-3 hours, and the deposition conditions of the Parylene layer include an evaporation temperature of 20-30 ℃ and an evaporation time of 10-30 hours.
In a third aspect, the invention provides a preparation method of a Parylene coating, which is used for the Parylene coating in the first aspect, and the preparation method of the Parylene coating comprises the steps of volatilizing a coupling agent in a vacuum environment, and then depositing a Parylene layer.
In some preferred embodiments of the present invention, the conditions under which the coupling agent volatilizes include a vacuum of 5 to 150Pa for a period of 1.5 to 5 hours.
In a fourth aspect, the invention provides a preparation method of a Parylene coating, which is used for the Parylene coating in the first aspect, and the preparation method of the Parylene coating comprises the steps of placing a coupling agent into an atomization chamber, atomizing the coupling agent in a vacuum heating environment, and then depositing a Parylene layer.
In some preferred embodiments of the present invention, the vacuum heating conditions include a vacuum of 13-33Pa and a heating temperature of 60-200deg.C.
In a fifth aspect, the present invention provides the use of a Parylene coating according to the first aspect for surface protection of a substrate to be coated.
In some preferred embodiments of the invention, the substrate to be plated is metal, glass or ceramic.
The beneficial effects are that:
It has been found that aminosilanes such as aminopropyl triethoxysilane have amino and triethoxysilane functional groups at both active ends, respectively, and that the coupling agent alone cannot function in the system of the Parylene (presumably it cannot react with the Parylene to undergo chemical bonding), since the Parylene is a free radical polymerization. The present invention has been further developed in this regard.
According to the technical scheme, the coupling agent with the specific structure of the carbon-carbon double bond end-capped A and the N group-capped B is particularly adopted, so that the adhesive force or the binding force of the Parylene layer on the substrate to be plated can be improved, the processing time for achieving high adhesive force is greatly shortened, the Parylene layer is firmly attached to the substrate to be plated in a short process time, various properties (such as protective property, lubricating property, barrier property and insulating pressure resistance) of the Parylene layer are endowed to the substrate to be plated, and the moisture-heat aging resistance of the Parylene coating is improved. The reason for this is presumably that the coupling agent of the specific structure has a catalytic action and a coupling action per se, the carbon-carbon double bond and the Parylene layer can undergo a free radical polymerization reaction to perform chemical bonding, and the coupling agent and the substrate to be plated are subjected to chemical bonding mainly by utilizing the coordination capability of N, so that a final product of a two-layer three-dimensional coating structure (one end of the coupling agent is the substrate, and the other end of the coupling agent is connected with the Parylene) is formed.
The invention also controls the coupling agent with proper N mass content, can control the N-containing group to be in a proper molecular weight range and proper high reactivity, matches with the Parylene, is beneficial to improving the adhesive force or the binding force of the Parylene layer on the substrate to be plated, and greatly shortens the processing time for achieving high adhesive force.
In addition, the adhesive force of the coupling agent in the prior art cannot be immediately improved after the coupling agent is attached and discharged from a furnace, and the coupling agent can ensure that the bonding force meets the industrial requirement only through a curing process. The special coupling agent can realize the state that the adhesive force is the maximum value after the adhesive coupling agent is discharged from the furnace, which is mainly beneficial to the Michael addition reaction between N and double bonds and the potential free radical chain transfer reaction, and the multiple possible reactions are overlapped, so that the integral reaction rate is accelerated, and the processing time for improving the adhesive force is shortened.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. Wherein the terms "optional" and "optionally" mean either comprising or not comprising (or may not be present).
In a first aspect, the invention provides a Parylene coating, which comprises a Parylene layer, wherein a coupling agent exists between the Parylene layer and a substrate to be plated, the coupling agent has the following general formula of A-M-B, and the mass content of N in the coupling agent is 3% -25%.
The coupling agent may contain 3% to 25% by mass of N, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25% and the like, and preferably 4% to 11.8% or 14.5% to 21.0%.
In some embodiments of the invention, A is selected from H 2C=C(R1) -COO-or H 2C=CH-R2 -, wherein R 1 is selected from H or alkyl having 1-3 carbon atoms and R 2 is selected from H, alkyl having 1-10 carbon atoms, or phenyl. In A, the double bond in acrylic ester and the double bond in allyl and vinyl can react with Parylene, and the reaction mechanism is free radical reaction. The A in the range of the acrylic ester is adopted, so that the reaction speed is high, the whole efficiency is high, and the adhesion or the binding force of the Parylene layer on the substrate to be plated can be improved. The A in the above range of alkenyl (such as allyl or vinyl) has higher temperature resistance, and is more beneficial to improving the humidity and heat aging resistance of the Parylene coating.
Preferably, R 1 is methyl, R 2 is methyl or phenyl, which makes the activity of the coupling agent higher, is more beneficial to improving the adhesive force or binding force of the Parylene layer on the substrate to be plated, and further shortens the processing time for achieving high adhesive force.
In some preferred embodiments of the invention, A is selected from、、Or (b). The adoption of the groups A is more beneficial to improving the adhesive force or the binding force of the Parylene layer on the substrate to be plated, and further shortens the processing time for achieving high adhesive force.
In some preferred embodiments of the invention, B comprises NH 2-、NR3R4-、NHR5-、NH2-(NH)s -CO-, thiourea groups orWherein the wavy line indicates a bond to M, wherein R 3 is selected from an alkyl group, an alkenyl group or a phenyl group having 1 to 9 carbon atoms, R 4 is selected from an alkyl group, an alkenyl group or a phenyl group having 1 to 9 carbon atoms, R 3 and R 4 cannot be phenyl groups at the same time, R 5 is selected from one of an alkyl group, an alkenyl group or a phenyl group having 1 to 9 carbon atoms, and s is 0to 2. The adoption of the B with the specific structure can coordinate a metal substrate, or corrode the substrate, or control the reactivity when being used together with other existing coupling agents, so that the reaction speed is slower than the permeation rate, and the adhesion of the surface of the substrate material with lower roughness is facilitated. B may include other groups in addition to these groups, as long as it is advantageous to enhance the binding force.
Wherein, R 3、R4、R5 is preferably alkyl, and the alkyl can be methyl, ethyl, propyl or alkyl chain with longer target carbon atom number and combination thereof, preferably the shorter the chain length is, the better the chain length is, the higher the reactivity is, and the improvement of the adhesive force or the bonding force of the Parylene layer on the substrate to be plated is facilitated.
It will be appreciated that B comprisesMeaning that the group N is attached to any one of A, M groups.
In some more preferred embodiments of the invention, B comprises、、、Or (b)Wherein the wavy line indicates a bond with M. The adoption of the groups B is more beneficial to improving the adhesive force or the binding force of the Parylene layer on the substrate to be plated, and further shortens the processing time for achieving high adhesive force.
Further preferably, B comprisesOr (b)Wherein the wavy line indicates a bond with M. The adhesive has certain corrosiveness due to the adoption of the primary amine functional group or the hydrazine functional group containing N, and can corrode certain micro-pore channels on the surface of a substrate (especially metal) to be plated, thereby being more beneficial to increasing the possibility of improving the adhesive force.
In some embodiments of the invention, M comprises- (CH 2)n1-、-CO-、-[O-(CH2)n2-O]n3 -),At least one group of (a) is provided. M may include other groups in addition to these groups, as long as it contributes to the improvement of the binding force.
Wherein n1 is 0-12, n2 is 1-5, n3 is 1-6;a, b is 1-3, c is 0-3, d is 0-8. By adopting the M with the proper structure, the adhesive force can be improved, the temperature resistance is promoted, and the F-type Parylene or HT-type Parylene can be matched for use at high temperature. The long-term use temperature of the F type Parylene can be 180 ℃. The long term use temperature of HT type Parylene can be at 350 ℃. n1 is 0 to 12 and may be, for example, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
The silicon-containing groups with the specific structure are used as the bridge between the two specific end caps A and B, and the silicon groups of three oxygen elements and the silicon groups of four oxygen elements are connected around the silicon element, so that the adhesion of the Parylene to the substrate to be plated is facilitated, and the heat resistance of the Parylene coating is improved.
The coupling agent A-M-B of the present invention may be obtained commercially or synthetically, and the synthetic method may be any synthetic method corresponding to the target structure, as long as the coupling agent of the target chemical formula is obtained, and may be used in the present invention.
Wherein comprisesThe coupling agent of (2) may be obtained commercially or synthetically, and any synthesis method may be used in the present invention, which may be referred to the corresponding existing synthesis method of the target structure.
Illustratively, the coupling agent is(Wherein a is 2, b is 1, c is 2, d is 5 in the corresponding M group), the corresponding raw materials comprise:
(abbreviated as A447), 、、、A corresponding specific embodiment is prepared by adding A447 into an organic solvent (such as isopropanol), adding tetraethyl orthosilicate and hexamethyldisiloxane, adding an acid (such as acetic acid), adding water to obtain a first mixture, mixing trimethoxy [3- (methylamino) propyl ] silane and 3-aminopropyl methyldimethoxy silane, neutralizing with an acid (such as acetic acid) to obtain a second mixture, adding the second mixture into a reactor of the first mixture before stirring and hydrolyzing, evaporating excessive organic solvent, adding an azeotropic reagent (such as toluene), azeotroping to remove excessive water, and obtaining the dry target N-containing coupling agent.
For example, the coupling agent isThe synthesis method comprises the steps of putting hydroxyethyl acrylate into a container, then putting IPDI (isophorone diisocyanate), DBTDL (dibutyl tin dilaurate), heating to 60-80 ℃ and stirring, cooling to room temperature, then slowly adding ethylenediamine in an ice bath (such as 0 ℃), and after the dripping is finished, reacting for a certain time (such as 1 h) after the temperature is raised to the room temperature, thus obtaining the target coupling agent.
For another example, the coupling agent isThe synthesis method comprises the steps of putting diethylene glycol monoacrylate into a container, then putting IPDI (isophorone diisocyanate), DBTDL (dibutyl tin dilaurate), heating to 60-80 ℃ and stirring for a certain time (such as 2-4 h), cooling to room temperature, then slowly adding ethylenediamine in an ice bath (such as 0 ℃), and reacting for a certain time (such as 1 h) after the dropwise addition, thus obtaining the target coupling agent.
It is understood that when n1 is 0, the coupling agent has the general formula A-B.
In some preferred embodiments of the present invention, the coupling agent is allylamine, acrylamide, diallylamine, triallylamine, N-methylallylamine, N' -diethylacrylamide, 4-acryloylmorpholine, N-dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, 2-acrylic acid hydrazide or. The optimized coupling agent is more beneficial to improving the adhesive force or the binding force of the Parylene layer on the substrate to be plated, and further shortens the processing time for achieving high adhesive force.
In some specific embodiments, the coupling agent is allylamine, and the allylamine has small molecular weight, strong penetrability and strong corrosiveness, can corrode micro-pore channels on the surface of a substrate (especially metal) to be plated, is convenient for riveting, and is more beneficial to improving the binding force of the coupling agent and the substrate to be plated.
In some specific embodiments, the coupling agent is 4-acryloylmorpholine, the reactivity of the coupling agent is relatively low, and a balance point can be found between the penetration time and the reactivity of the coupling agent, so that the coupling agent is more beneficial to improving the binding force on the surface of the low-roughness substrate, and meanwhile, the processing time is greatly shortened.
In some preferred embodiments of the invention, the coupling agent is 0.5% -7%, preferably 0.5% -5%, further preferably 0.5% -3.5%, more preferably 0.5% -2%, further preferably 0.5% -1.5% of the mass of the Parylene layer. The proper proportioning amount of the coupling agent and the Parylene can improve the total content of the Parylene in the Parylene coating, is more beneficial to improving the barrier property of the Parylene coating, is more beneficial to improving the binding force on the surface of the low-roughness substrate, and greatly shortens the processing time.
The coupling agent of the present invention is applicable to any type of Parylene layer, for example, C-type, N-type, F-type or HT-type Parylene, etc., and may be used in the present invention.
The coupling agent of the invention is applicable to a wide preparation process, and can be applicable to any preparation method of the existing Parylene coating, such as a soaking method, a volatilizing method, an atomizing method and the like.
In a second aspect, the invention provides a preparation method of a Parylene coating, which is used for the Parylene coating in the first aspect, and the preparation method of the Parylene coating comprises the steps of immersing a substrate to be plated in an organic solution containing a coupling agent, drying, and depositing a Parylene layer. The method has the advantages that the quantity of the upper coupling agent is relatively uniform, and the adhesive force of the prepared Parylene coating product is relatively stable.
In some preferred embodiments of the present invention, the organic solution containing the coupling agent is obtained by dissolving the coupling agent in an organic solvent.
The organic solvent may be at least one of isopropyl alcohol, ethanol, toluene, acetone, butanone, and the like, for example.
Preferably, the mass concentration of the coupling agent in the organic solution containing the coupling agent is 0.5wt% to 5wt%, preferably 1wt% to 5wt%. The coupling agent with proper concentration is more beneficial to improving the barrier property of the Parylene coating.
Preferably, the conditions for depositing the Parylene layer include an evaporation temperature of 20-30 ℃ and an evaporation time of 10-30 hours, preferably 20-30 hours. The adoption of the condition of preferably depositing the Parylene layer is more beneficial to improving the binding force.
In the second aspect, the soaking time is shorter if the substrate has no holes, and longer if the substrate has holes. In some preferred embodiments of the invention, the soaking time is 1-2 hours.
Preferably, the drying conditions comprise a drying temperature of 40-80 ℃ and a drying time of 1-3h.
In a third aspect, the invention provides a preparation method of a Parylene coating, which is used for the Parylene coating in the first aspect, and the preparation method of the Parylene coating comprises the steps of volatilizing a coupling agent in a vacuum environment, and then depositing a Parylene layer. The coupling agent is relatively easy to volatilize, can be suitable for the volatilization method of the third aspect, and is suitable for some sensitive devices or products which cannot be subjected to any surface treatment. And one end of the coupling agent is carboxyl or phosphate group, which is conventionally adopted in the prior art, and is extremely difficult to gasify due to strong intramolecular hydrogen bonds.
In some preferred embodiments of the third aspect of the present invention, the conditions under which the coupling agent volatilizes include a vacuum of 5 to 150Pa, preferably 5 to 40Pa, more preferably 13 to 33Pa, for a period of 1.5 to 5 hours.
In the third aspect, the coupling agent is first evaporated (or heated), then the Parylene is deposited, and the ratio of the respective evaporation and deposition times is selected depending on the volatility of the coupling agent, and the heating (or evaporation) time of the coupling agent may be specifically selected according to the target time required for the deposition thickness of the Parylene. In general, assuming that 20 μm thick Parylene is deposited, the time for depositing the Parylene is typically 10 hours, and the time for evaporating the coupling agent is typically 1.5 to 5 hours. Preferably, the coupling agent is heated for a period of time ranging from 1.5 to 5 hours.
In a fourth aspect, the invention provides a preparation method of a Parylene coating, which is used for the Parylene coating in the first aspect, and the preparation method of the Parylene coating comprises the steps of placing a coupling agent into an atomization chamber, atomizing the coupling agent in a vacuum heating environment, and then depositing a Parylene layer. The coupling agent can be atomized under the relatively low temperature rising condition, can be suitable for the atomization method of the fourth aspect, and is suitable for some sensitive devices or products which cannot be subjected to any surface treatment. And one end of the coupling agent is carboxyl or phosphate group, which is conventionally adopted in the prior art, and is extremely difficult to atomize due to strong intramolecular hydrogen bonds.
In the second to fourth aspects, the ratio of the deposition amount of the Parylene to the coupling agent can be adjusted in a suitable range by controlling the coupling agent and the amount of the Parylene to be fed.
In some preferred embodiments of the fourth aspect of the present invention, the vacuum heating conditions include a vacuum of 13 to 33Pa and a heating temperature of 60 to 200℃and preferably 100 to 200 ℃. The vacuum heating time is generally continuous, for example, about 10-24 hours before and after the deposition of the Parylene, depending on the thickness of the deposited Parylene.
In the second to fourth aspects of the present invention, chemical Vapor Deposition (chemical vapor deposition, abbreviated as CVD) is used to deposit the Parylene layer, and PARYLENE N, PARYLENE C, PARYLENE F or PARYLENE HT is used as a raw material, and the deposition process can be respectively performed according to the prior art, for example, the deposition of the Parylene is generally divided into three temperature areas, namely, a first temperature area called an evaporation area, the temperature is generally controlled to 150 ℃, a second temperature area called a cracking area, the temperature is controlled to 690 ℃, a third temperature area called a deposition area, and the temperature is controlled to 25 ℃, which are not described in detail herein.
In a fifth aspect, the present invention provides the use of a Parylene coating according to the first aspect for surface protection of a substrate to be coated.
In some preferred embodiments of the present invention, the substrate to be plated is any one of metal, glass, ceramic. The metal may be, for example, copper, silver, aluminum, gold-plated stainless steel sheet, or the like. The ceramic may be, for example, an oxide or nitride.
The following detailed description of the embodiments of the invention is exemplary and is merely illustrative of the invention and not to be construed as limiting the invention.
Example 1
The coupling agent is N-methylallylamine. The mass content of N in the coupling agent is 19.68%.
The preparation method of the Parylene coating comprises the following steps:
The coupling agent was dissolved in isopropanol to prepare a 3% soak solution. Immersing a substrate to be plated (particularly a glass slide, a stainless steel sheet, an aluminum sheet, a gold-plated sheet and a copper sheet respectively to form a Parylene coating) in the immersion liquid for 1h, then drying at 65 ℃ for 1h to obtain a device to be plated, then placing the device to be plated into a furnace, and depositing a Parylene layer by CVD by using PARYLENE N as a raw material (the commercial manufacturer is Suzhou subfamily chemical agent Co., ltd.) under the conditions that the evaporation temperature is 25 ℃ and the evaporation time is 24h. The mass dosage ratio of the Parylene and the coupling agent is 15:1.
Example 2
The method of the reference example 1 is different in preparation method, specifically, the vacuum degree is 20Pa in a vacuum environment, the coupling agent is naturally volatilized for 2 hours in a normal-temperature vacuum environment, after the coupling agent is volatilized, a Parylene layer is deposited by CVD (the deposition process is the same as that of the example 1), and the volatilized coupling agent and the Parylene are simultaneously reacted on the surface of a substrate to be plated, so that the Parylene coating with good binding force is obtained.
Example 3
The method of example 1 was referred to, except that the preparation method was different, specifically, the coupling agent was placed in an atomization chamber, the coupling agent was atomized in a vacuum heating environment at a vacuum degree of 20Pa at a heating temperature of 150 ℃ for 2 hours, and then a Parylene layer was deposited by CVD (deposition process was the same as in example 1), so that the coupling agent and the Parylene were simultaneously reacted on the surface of the substrate to be plated, to obtain a Parylene coating having a good bonding force.
Example 4
The procedure of example 1 was carried out, except that 4-acryloylmorpholine (commercial manufacturer was national pharmaceutical chemicals Co., ltd.) was used as the coupling agent, and the mass content of N in the coupling agent was 9.91%, the others were unchanged.
Example 5
The procedure of example 1 is followed, except that the coupling agent is(Corresponding to the M groups, a is 2, b is 1, c is 2, d is 5), the mass content of N in the coupling agent is 4.03%, and the other is unchanged. The preparation process of the coupling agent is as follows:
10g will be (Commercial manufacturer: momentive Performance Materials Inc. (abbreviated as "Mai-Tong Co., ltd.) (abbreviated as A447)) was added to 226g of isopropyl alcohol, 19.56g of tetraethylorthosilicate (commercial manufacturer: national medicine group chemical reagent Co., ltd.) was added, 15g of hexamethyldisiloxane (commercial manufacturer: national medicine group chemical reagent Co., ltd.) was added to 8mL of acetic acid to obtain a first mixture, 8.9 g of trimethoxy [3- (methylamino) propyl ] silane (commercial manufacturer: national medicine group chemical reagent Co., ltd.) and 15.1. 15.1 g of 3-aminopropyl methyl dimethoxy silane (commercial manufacturer: nanjing Nernd. New material technology Co.) were mixed, neutralized with 9 mL acetic acid, a second mixture was obtained after the neutralization was added to the reactor of the first mixture before the completion of the hydrolysis reaction by stirring for 3 hours, and then 100mL of toluene was added to obtain a dry target N-containing coupling agent by rotary evaporation of the excess isopropyl alcohol.
Example 6
The procedure of example 1 was carried out, except that the coupling agent was N, N' -diethylacrylamide (commercially available manufacturer was national pharmaceutical chemicals Co., ltd.), and the mass content of N in the coupling agent was 11.00%, the others were unchanged.
Example 7
The procedure of example 1 was carried out, except that the coupling agent was diallylamine (commercial manufacturer was national medicine group chemical reagent Co., ltd.), and the N content of the coupling agent was 14.41% by mass, with the other matters remaining unchanged.
Example 8
The procedure of example 1 was carried out, except that the coupling agent was triallylamine (commercial manufacturer was national medicine group chemical agent Co., ltd.), and the N content by mass in the coupling agent was 10.20%, the others were unchanged.
Example 9
The procedure of example 1 was carried out, except that the coupling agent was allylthiourea (commercial manufacturer was national drug group chemical reagent Co., ltd.), and the N content of the coupling agent was 12.05% by mass, with the other matters remaining unchanged.
Example 10
The procedure of example 1 is followed, except that the coupling agent isThe mass content of N in the coupling agent is 14.06%, and the other components are unchanged. The preparation method of the coupling agent comprises the following steps:
10g of hydroxyethyl acrylate was put into a 3-neck flask, then 17.1g IPDI,0.031g DBTDL was put into the flask, heated at 70℃and stirred for 3 hours, cooled to room temperature, and then 4.6g of ethylenediamine was slowly added in an ice bath at 0 ℃. After the completion of the dropwise addition, the reaction was carried out at room temperature for 1 hour to obtain a coupling agent.
Wherein hydroxyethyl acrylate (national medicine group chemical Co., ltd.), IPDI (isophorone diisocyanate) (Wanhua chemical Co., ltd.), DBTDL (dibutyl tin dilaurate) (national medicine group chemical Co., ltd.), ethylenediamine (national medicine group chemical Co., ltd.)
Example 11
The procedure of example 1 is followed, except that the coupling agent isThe mass content of N in the coupling agent is 12.66%, and the other components are unchanged. The preparation method of the coupling agent comprises the following steps:
10g of diethylene glycol monoacrylate was put into a 3-neck flask, then 13.88g IPDI,0.027g DBTDL was put into the flask, heated at 70℃and stirred for 3 hours, cooled to room temperature, and then 3.75g of ethylenediamine was slowly added at 0℃in an ice bath. After the completion of the dropwise addition, the reaction was carried out at room temperature for 1 hour. Obtaining the coupling agent.
Among them, diethylene glycol monoacrylate (Hannong Chemicals), IPDI (isophorone diisocyanate) (Wanhua chemical group Co., ltd.), DBTDL (dibutyltin dilaurate) (national medicine group chemical agent Co., ltd.), ethylenediamine (national medicine group chemical agent Co., ltd.).
Example 12
The procedure of example 1 was followed, except that the amount of coupling agent was varied, and the ratio of the amount of Parylene to the amount of coupling agent layer was adjusted to be 25:1.
Example 13
The method of example 1 was performed by adjusting the deposition time of the Parylene layer, specifically controlling the vapor deposition pressure, and shortening the vapor deposition time to 15 hours in the immersion method of example 1.
Example 14
The procedure of example 1 was followed, except that the vacuum degree at which the coupling agent volatilized was adjusted to 100Pa in the preparation method of example 2.
Example 15
The procedure of example 1 was followed, except that in the preparation of example 3, the key process parameters, heating temperature, were adjusted to 60 ℃.
Example 16
The procedure of example 1 was carried out, except that the coupling agent was N, N-dimethylaminoethyl acrylate (commercial manufacturer was national pharmaceutical Co., ltd.) and the N content of the coupling agent was 9.78% and the others were unchanged.
Example 17
The procedure of example 1 was carried out, except that the coupling agent was dimethylaminoethyl methacrylate (commercial manufacturer was national pharmaceutical chemicals Co., ltd.) and the N content of the coupling agent was 8.91% and the others were unchanged.
Example 18
The procedure of example 1 was carried out, except that the coupling agent was acrylamide (commercial manufacturer was national medicine group chemical reagent Co., ltd.), and the N content of the coupling agent was 19.69%, the others were unchanged.
Example 19
The procedure of example 1 was followed, except that 2-acrylic hydrazide (commercial manufacturer was national chemical reagent Co., ltd.) was used as the coupling agent, and the N content of the coupling agent was 16.26% and the others were unchanged.
Comparative example 1
The procedure of example 1 was followed, except that the coupling agent was gamma-aminopropyl triethoxysilane (commercial manufacturer is national pharmaceutical chemicals Co., ltd.), and the N content of the coupling agent was 6.32% by mass, with the other matters remaining unchanged. It contains no carbon-carbon double bond and can not be subjected to free radical polymerization reaction with the Parylene layer to carry out chemical bonding.
Comparative example 2
The procedure of example 1 was followed, except that the coupling agent was A174 ((3-Methacryloxypropyl) trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, commercially available from Guo Chemicals Co., ltd.) and the others were unchanged.
Comparative example 3
The procedure of example 1 was followed except that the coupling agent was trimethoxy [3- (methylamino) propyl ] silane (commercially available from Guo Chemicals Co., ltd.). The mass content of N in the coupling agent is 7.24%.
Comparative example 4
The procedure of example 1 was followed except that the coupling agent was [3- (N, N-dimethylamino) propyl ] trimethoxysilane (commercially available from Guo Chemicals Co., ltd.). The mass content of N in the coupling agent is 6.75%.
Comparative example 5
The procedure of example 1 is followed, except that the coupling agent is. The coupling agent had an N content of 1.07%. The preparation method of the coupling agent comprises the following steps:
10g of bis (3-trimethoxysilylpropyl) amine (commercial manufacturer: national chemical reagent Co., ltd.) was added to 186g of isopropyl alcohol, 21.37g of hexamethyldisiloxane (commercial manufacturer: national chemical reagent Co., ltd.) and 8.69g of vinyltrimethoxysilane (commercial manufacturer: national chemical reagent Co., ltd.) were added, 14.07g of dimethyldimethoxysilane (commercial manufacturer: national chemical reagent Co., ltd.) was added to 6mL of acetic acid and 18g of water was added to obtain a first mixture, bis (3-trimethoxysilylpropyl) amine (commercial manufacturer: national chemical reagent Co., ltd.) was neutralized with 1.75 mL acetic acid and a second mixture was obtained after the neutralization was completed, and after the second mixture was put into the reactor of the first mixture, the reaction was stirred for 3 hours, surplus isopropyl alcohol was rotationally evaporated, and then 100mL of toluene was added to obtain a dry coupling agent containing N as an azeotropic mixture.
Comparative example 6
The procedure of example 1 was followed except that the coupling agent was methyl methacrylate (commercial manufacturer was national chemical reagent Co., ltd.).
Test case
The Parylene coatings obtained in the above examples and comparative examples were subjected to the respective performance tests shown in table 1, and the results are shown in table 1. The binding force is tested according to a standard ASTM D3359 hundred-grid test method, the binding force grade is shown in table 1, the higher the grade number, the stronger the binding force, the hundred-grid test method comprises scribing the surface of the coating according to the standard, then adhering with a specific adhesive tape, and judging whether the coating can be adhered by the adhesive tape or not. In addition, because the atmosphere of different heights in the CVD deposition furnace of the Parylene coating can be different, the inside of the furnace is equally divided into 5 different heights in the corresponding CVD deposition process in each example, corresponding slide sheets (namely, glass slides, stainless steel sheets, aluminum sheets, gold-plated sheets and copper sheets) are respectively placed at different heights to obtain five groups of samples, five groups of grade data are obtained according to the standard test, the data with higher grade occurrence frequency is taken as the final data to be measured, and the data with higher grade occurrence frequency is taken as the final data to be measured if the data with higher grade occurrence frequency is 5B, 4B and 5B of the slide sheets.
Wherein, the preservation condition of discharging for 2 hours or discharging for 3 days is that the temperature is 25 ℃ and the humidity is 50%, and the binding force is tested according to the standard after the preservation target time.
The binding force after 2 hours at 150℃is a binding force measured according to the above criteria after aging in a dry box at 150℃for 2 hours after 3 days in the oven.
Double 85% indicates the binding force measured according to the above criteria after aging for 120 hours in an environment of 85% humidity at a temperature of 85 ℃ after 3 days in the oven.
TABLE 1
Table 1 (Xueqian Table 1)
Compared with the comparative example, the embodiment of the invention can improve the binding force of the Parylene layer on the substrate to be plated, and greatly shorten the processing time for achieving high adhesion, thereby realizing the stable adhesion of the Parylene layer on the substrate to be plated in a shorter processing time. Among them, comparative example 2 is a coupling agent commonly used in the industry, which reacts with trimethoxysilane at the active end of the substrate, and needs to react with water to be effective, and under the condition of no catalyst effect, the trimethoxysilane reacts with water for a relatively slow time, and the binding force is obviously weaker than that of the examples of the invention.
Further, according to example 1 and examples 9-19, the preferred specific structure coupling agent or specific process scheme of the present invention is adopted to further facilitate the improvement of the binding force of the Parylene layer on the substrate to be plated.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (12)
1. A Parylene coating comprises a Parylene layer, and is characterized in that a coupling agent is arranged between the Parylene layer and a substrate to be plated, wherein the coupling agent comprises a general formula A-M-B, the mass content of N in the coupling agent is 3-25 percent,
A is selected from H 2C=C(R1) -COO-or H 2C=CH-R2-,R1 is selected from H or alkyl with 1-3 carbon atoms, and R 2 is selected from H, alkyl with 1-10 carbon atoms or phenyl;
B comprises NH 2-、NR3R4-、NHR5-、NH2-(NH)s -CO-, thiourea groups or Wherein the wavy line indicates a connecting key;
Wherein R 3 is selected from alkyl, alkenyl or phenyl with 1-9 carbon atoms, R 4 is selected from alkyl, alkenyl or phenyl with 1-9 carbon atoms, R 3 and R 4 cannot be phenyl at the same time, R 5 is selected from one of alkyl, alkenyl or phenyl with 1-9 carbon atoms, and s is 0-2;
M comprises- (CH 2)n1-、-CO-、-[O-(CH2)n2-O]n3 -), At least one of the groups of (a) is,
Wherein n1 is 0-12, n2 is 1-5, n3 is 1-6;a, b is 1-3, c is 0-3, d is 0-8.
2. A Parylene coating as set forth in claim 1, wherein,
A is selected from、、Or (b);
And/or the number of the groups of groups,
B comprises、、、Or (b);
Wherein the wavy line indicates a connection key.
3. The Parylene coating of claim 2, wherein B comprisesOr (b)Wherein the wavy line indicates a connection key.
4. The Parylene coating of claim 1, wherein the coupling agent is allylamine, acrylamide, diallylamine, triallylamine, N-methylallylamine, N' -diethylacrylamide, 4-acryloylmorpholine, acrylic-N, N-dimethylaminoethyl ester, dimethylaminoethyl methacrylate, 2-acrylic hydrazide, or。
5. The Parylene coating of claim 1, wherein the coupling agent is 0.5% -7% of the mass of the Parylene layer.
6. Use of a Parylene coating as set forth in any one of claims 1-5 for surface protection of a substrate to be plated, the substrate to be plated being metal, glass or ceramic.
7. A method for preparing a Parylene coating, characterized in that it is used for preparing a Parylene coating according to any one of claims 1-5, and the preparation method of the Parylene coating comprises immersing a substrate to be plated in an organic solution containing a coupling agent, followed by drying, and then depositing a Parylene layer.
8. The preparation method of the Parylene coating according to claim 7, wherein the organic solution containing the coupling agent is obtained by dissolving the coupling agent in an organic solvent, and the mass concentration of the coupling agent in the organic solution containing the coupling agent is 0.5-5 wt%;
And/or the number of the groups of groups,
The soaking time is 1-2h, the drying condition comprises that the drying temperature is 40-80 ℃ and the time is 1-3h, and the condition for depositing the Parylene layer comprises that the evaporation temperature is 20-30 ℃ and the evaporation time is 10-30h.
9. A method for preparing a Parylene coating, characterized in that it is used for preparing the Parylene coating according to any one of claims 1-5, and the preparation method of the Parylene coating comprises volatilizing a coupling agent under a vacuum environment, and then depositing a Parylene layer.
10. The method for preparing a Parylene coating according to claim 9, wherein the conditions for volatilizing the coupling agent include a vacuum degree of 5-150Pa for 1.5-5h.
11. A method for preparing a Parylene coating, characterized in that it is used for preparing a Parylene coating as set forth in any one of claims 1-5, and the preparation method of the Parylene coating comprises placing a coupling agent into an atomization chamber, atomizing the coupling agent in a vacuum heating environment, and then depositing a Parylene layer.
12. The method for preparing a Parylene coating according to claim 11, wherein the vacuum heating conditions include a vacuum degree of 13-33Pa and a heating temperature of 60-200 ℃.
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