CN118719508B - A Parylene coating containing a complex coupling agent and its preparation method and application - Google Patents
A Parylene coating containing a complex coupling agent and its preparation method and application Download PDFInfo
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- CN118719508B CN118719508B CN202411217162.0A CN202411217162A CN118719508B CN 118719508 B CN118719508 B CN 118719508B CN 202411217162 A CN202411217162 A CN 202411217162A CN 118719508 B CN118719508 B CN 118719508B
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- 239000007822 coupling agent Substances 0.000 title claims abstract description 250
- 229920000052 poly(p-xylylene) Polymers 0.000 title claims abstract description 115
- 238000000576 coating method Methods 0.000 title claims abstract description 55
- 239000011248 coating agent Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 65
- 239000000758 substrate Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 230000003301 hydrolyzing effect Effects 0.000 claims description 25
- 238000009833 condensation Methods 0.000 claims description 21
- 230000005494 condensation Effects 0.000 claims description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- -1 methacryloyl Chemical group 0.000 claims description 6
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 6
- UVBBCQLPTZEDHT-UHFFFAOYSA-N pent-4-en-1-amine Chemical compound NCCCC=C UVBBCQLPTZEDHT-UHFFFAOYSA-N 0.000 claims description 6
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- DVYVMJLSUSGYMH-UHFFFAOYSA-N n-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CNCCC[Si](OC)(OC)OC DVYVMJLSUSGYMH-UHFFFAOYSA-N 0.000 claims description 4
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 3
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 claims description 3
- 229960001748 allylthiourea Drugs 0.000 claims description 3
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 claims description 3
- VPJDULFXCAQHRC-UHFFFAOYSA-N prop-2-enylurea Chemical compound NC(=O)NCC=C VPJDULFXCAQHRC-UHFFFAOYSA-N 0.000 claims description 3
- 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
- IXPWKHNDQICVPZ-UHFFFAOYSA-N 2-methylhex-1-en-3-yne Chemical compound CCC#CC(C)=C IXPWKHNDQICVPZ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims 3
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 claims 2
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 claims 1
- QISNULGCGWEUKY-UHFFFAOYSA-N n-ethyl-2-methylidenebutanamide Chemical compound CCNC(=O)C(=C)CC QISNULGCGWEUKY-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 89
- 239000000853 adhesive Substances 0.000 abstract description 38
- 230000001070 adhesive effect Effects 0.000 abstract description 38
- 230000008569 process Effects 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 230000009286 beneficial effect Effects 0.000 description 10
- 239000003814 drug Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000005137 deposition process Methods 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical group CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 125000005371 silicon functional group Chemical group 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
- 230000003068 static effect Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 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
- 239000003039 volatile agent Substances 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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- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention belongs to the technical field of Parylene material coatings, and in particular relates to a Parylene coating containing a compound coupling agent, a preparation method and application thereof, wherein the Parylene coating comprises a Parylene layer, a compound coupling agent exists between the Parylene layer and a substrate to be plated, the compound coupling agent comprises a silane coupling agent and an N-containing coupling agent, and the mass ratio of the silane coupling agent to the N-containing coupling agent is 1: (0.2-3), and the compound coupling agent is respectively chemically bonded with the Parylene layer and the substrate to be plated. The invention can obviously improve the adhesive force, can achieve the maximum adhesive force only by a short process time, and has good heat resistance, excellent uniformity of all samples in one batch and excellent stability among multiple batches.
Description
Technical Field
The invention belongs to the technical field of Parylene material coatings, and particularly relates to a Parylene coating containing a compound coupling agent, and a preparation method and application thereof.
Background
The Parylene layer provides various properties such as protective property, lubricating property, barrier property and insulating pressure resistance, and is a novel coating of special materials. Parylene deposition is a process employing vapor deposition, and Parylene itself has extremely strong water vapor barrier efficiency. Since the Parylene material (Parylene, also called Parylene) is symmetrical (has weak polarity), the adhesive force generated in the process of converting the gas state into the solid state is just like the liquid state wax into the solid state wax, and the adhesive force can be a little, but the adhesive strength is difficult to be used for industrialization.
In the prior art, one way of acting on the substrate end is to allow the coupling agent with smaller molecular weight to penetrate into the pores of the substrate when the surface roughness of the substrate end material is larger, 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.
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 taken out of the furnace after soaking and evaporation, the adhesive force after the discharging can not be immediately improved generally, and the bonding force can be ensured to meet the industrial requirement only after a curing process, namely, the silane coupling agent and water vapor react for 3-4 days. The strength of the binding force is usually judged by using a hundred-grid method, the binding force just discharged from the furnace is generally in the level of 2-3B, and after the binding force is placed for 3-4 days, the binding force can be increased to the level of 4-5B. That is, the existing silane coupling agent has long process time for improving the adhesive force. Moreover, the uniformity of adhesion across the cavity, as well as the batch-to-batch stability, is poor.
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 adhesive force in the prior art, and provides a Parylene coating containing a compound coupling agent, a preparation method and application thereof, the Parylene coating containing the compound coupling agent can remarkably improve the adhesive force, can achieve the maximum adhesive force only by a short process time, and has good heat resistance, excellent uniformity of all samples in one batch and excellent stability among multiple batches.
In order to achieve the above purpose, in a first aspect, the present invention provides a Parylene coating layer containing a compound coupling agent, including a Parylene layer, wherein a compound coupling agent exists between the Parylene layer and a substrate to be plated, the compound coupling agent includes a silane coupling agent and an N-containing coupling agent, the mass ratio of the silane coupling agent to the N-containing coupling agent is 1 (0.2-3), and the compound coupling agent is respectively chemically bonded with the Parylene layer and the substrate to be plated;
The silane coupling agent is selected from gamma-aminopropyl triethoxysilane, ethyl silicate and
(Abbreviated as A274),(Abbreviated as A174),(Abbreviated as A151),、、、、、At least one of them or its corresponding hydrolytic condensate.
The N-containing coupling agent has the following general formula of A- (M) p-B, wherein p=0 or 1, and the mass content of N in the N-containing coupling agent is 1.5% -20%, preferably 3% -20%.
Wherein A comprises、、、、、、、、、Wherein the wavy line represents a bond to M;
b comprises 、、、、、Thiourea group,R 1 is selected from H or alkyl with 1-9 carbon atoms, R 2 is selected from H or alkyl with 1-9 carbon atoms, wherein the wavy line represents a bond with M;
M comprises 、-CO-、、、One of the above-mentioned materials is used for the preparation of the liquid,
Wherein n1 is 1-12, n2 is 1-6, n3 is 1-6;a is 1-6, b is 0-3, c is 0-3, d is 0-8.
In some preferred embodiments of the present invention, the N-containing coupling agent is at least one of N-methyl-3-aminopropyl trimethoxysilane, N-diethylaminoethyl acrylate, di, N' -diethylacrylamide, N-methylallylamine, allylurea, methacryloylhydrazide, 4-acryloylmorpholine, diallylamine, triallylamine, allylthiourea, N-dimethylallylamine, 4-penten-1-amine, 2-aminoethyl methacrylate.
In some preferred embodiments of the present invention, the N-containing coupling agent is at least one of methacryloyl hydrazide, diallyl amine, triallyl amine, N-dimethylallyl amine, 4-penten-1-amine, 2-aminoethyl methacrylate.
In some preferred embodiments of the present invention, the compounded coupling agent is 0.5% -32% of the mass of the Parylene layer.
In a second aspect, the invention provides a preparation method of a Parylene coating containing a compound coupling agent, which is used for preparing the Parylene coating containing the compound coupling agent in the first aspect. And the preparation method of the Parylene coating containing the complexing agent comprises the following steps:
dissolving an N-containing coupling agent and a silane coupling agent in an alcohol solvent and water for mixing, or carrying out hydrolytic condensation on the N-containing coupling agent, the silane coupling agent and the water to obtain a solution containing a compound coupling agent;
then the substrate to be plated is soaked in the solution containing the compound coupling agent for 10-120min, then dried, and then the Parylene layer is deposited.
In some preferred embodiments of the present invention, the hydrolytic condensation conditions include a temperature of the hydrolytic condensation of room temperature to 60 ℃, a mass amount of water of 0.1 to 20wt% of the total amount of the N-containing coupling agent and the silane coupling agent, and a time of the hydrolytic condensation of 0.5 to 24 hours.
In some preferred embodiments of the second aspect of the present invention, the mass concentration of the compounding coupling agent in the solution containing the compounding coupling agent is 0.5wt% to 9wt%, preferably 1wt% to 5wt%.
In some preferred embodiments of the second aspect of the present invention, the conditions for drying include a drying temperature of 40-100 ℃ for a period of 1-3 hours.
In a third aspect, the present invention provides a method for preparing a Parylene coating containing a compound coupling agent, which is used for preparing the Parylene coating containing a compound coupling agent in the first aspect, and the method for preparing the Parylene coating containing a compound coupling agent comprises:
dissolving an N-containing coupling agent and a silane coupling agent in an alcohol solvent and water for mixing, or carrying out hydrolytic condensation on the N-containing coupling agent, the silane coupling agent and the water to obtain a solution containing a compound coupling agent;
Then in vacuum environment, the compound coupling agent in the solution containing the compound coupling agent is controlled to volatilize, so that the volatilized compound coupling agent reacts on the surface of the substrate to be plated, and then a Parylene layer is deposited, so that the volatilized compound coupling agent and the Parylene react on the surface of the substrate to be plated.
In a fourth aspect, the present invention provides a method for preparing a Parylene coating containing a compound coupling agent, which is used for preparing the Parylene coating containing a compound coupling agent in the first aspect, and the method for preparing the Parylene coating containing a compound coupling agent comprises:
dissolving an N-containing coupling agent and a silane coupling agent in an alcohol solvent and water for mixing, or carrying out hydrolytic condensation on the N-containing coupling agent, the silane coupling agent and the water to obtain a solution containing a compound coupling agent;
placing the solution containing the compound coupling agent into an atomization chamber, volatilizing the compound coupling agent in a vacuum heating environment, and enabling the volatilized compound coupling agent to react on the surface of the substrate to be plated; and then depositing a Parylene layer, so that the compound coupling agent and the Parylene react on the surface of the substrate to be plated.
In some preferred embodiments of the fourth aspect of the present invention, the vacuum heating conditions include a vacuum of 50 to 300mTorr and a temperature of 40 to 250 ℃.
In a fifth aspect, the invention provides an application of the Parylene coating containing the compound coupling agent in the first aspect in surface protection of a substrate to be plated.
Further preferably, the substrate to be plated is any one of metal, ceramic and glass.
The beneficial effects are that:
It has been found that although N-containing coupling agents can promote adhesion between substrates to be plated (e.g., metal substrates and ceramic substrates) and Parylene, N-containing coupling agents of different structures have different reactivity, especially N-containing end group B reactivity, which can be understood from two dimensions, the first dimension being the ability to catalyze reactions, such as chain transfer reactions, michael additions, the ability to catalyze siloxane hydrolysis, etc., and the second dimension being the ability to corrode, generally speaking, the greater the nucleophilicity, the greater the ability to corrode, and the greater the corresponding adhesion (or adhesion). Some N-containing end groups B are unsuitable in structure, poor in reactivity, incapable of effectively improving adhesive force and poor in heat resistance. Based on this, the present invention has been further studied to bring the present invention.
According to the technical scheme, aiming at the N-containing coupling agent with a specific structure, which has proper molecular weight, volatility, reactivity and temperature resistance, the compound coupling agent which can form a specific composition with a specific silane coupling agent can play a role in synergy, on one hand, the end group B of the N-containing coupling agent has coordination capability and can form coordination with a substrate to be plated, the end group A of the N-containing coupling agent contains carbon-carbon double bonds or the N-containing coupling agent without the carbon-carbon double bonds end group A and the silane coupling agent with double bonds generate a new coupling agent in situ through a silane hydrolysis reaction, the new coupling agent has the capability of connecting one end with a double bond and one end with a substrate, and the silane hydrolysis reaction generates a new coupling agent in situ, such as:
The N-containing coupling agent can catalyze the hydrolysis reaction of the alkoxysilane in the silane coupling agent by utilizing the coordination capacity and the catalysis capacity of N in the specific end group B when the N-containing coupling agent forms coupling by itself, so that the adhesive force structure of the silane coupling agent and the substrate to be plated is promoted to be increased, the adhesive force is accelerated, the N-containing coupling agent of the specific structure has proper permeability, the stable riveting effect can be formed after the N-containing coupling agent is completely permeated, the batch stability and the uniformity are facilitated, the excellent effect of the adhesive force multiplication is achieved, meanwhile, the maximum adhesive force can be achieved only by a short process time, the heat resistance is excellent, and the good heat resistance, the uniformity of all samples in one batch and the stability among multiple batches are excellent. The N-containing coupling agent selects N-containing functional groups with proper reactivity as B, and is matched with silane coupling agent with proper structure, so that the permeation rate and the reaction rate can be balanced, and the adhesion force can be improved cooperatively, especially on the surface with low roughness, namely the surface with small pore channels or less pore channels. Under the same conditions, if the B group is not suitable, resulting in a reaction rate greater than the permeation rate, the adhesion will be poor.
For example, if a separate silane coupling agent such as A174 is used on the surface of a substrate to be plated (such as a metal substrate) with high roughness, the molecular weight is too low, and the rivet formed by the silane coupling agent can penetrate into the substrate to be plated, but the rivet is too small, so that the pore canal of the substrate to be plated is not blocked, and the substrate to be plated is pulled off as soon as pulling, the adhesion is poor, and is easy to fall off, and N in the N-containing coupling agent can form coordination with metal, particularly Cu or Fe. When the N-containing coupling agent and the silane coupling agent such as A174 are compounded for use, the N-containing coupling agent can catalyze the hydrolysis reaction of the alkoxy silane in the silane coupling agent, so that the silane coupling agent can rapidly form a three-dimensional network structure to block the pore canal of the substrate to be plated, a physically large-size riveting structure is formed, and meanwhile, the N-containing coupling agent can be chemically bonded with the substrate to be plated, so that better adhesive force can be realized under the synergistic effect, the maximum adhesive force can be achieved only by a shorter process time, and the high heat resistance, the uniformity of all samples in one batch and the high stability among multiple batches are achieved.
According to the invention, the silane coupling agent and the N-containing coupling agent with proper mass ratio are adopted, and the specific N-containing coupling agent with proper N mass content is matched, so that the permeation rate and the reaction rate can be balanced, the synergistic effect can be brought into play to the maximum, and the adhesive force can be obviously improved. This is because if the mass ratio and/or the N mass content are not suitable, such as high permeation rate, low reaction speed, slow onset of mechanical properties, poor adhesion, such as low permeation rate, fast reaction speed, fast onset of mechanical properties, but low final peel strength, poor adhesion, poor stability. If the proportion of the silane coupling agent is low, the crosslinking degree is low, the adhesive force is poor, and if the proportion of the silane coupling agent is high, the post-treatment operation is complex.
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 containing a compound coupling agent, which comprises a Parylene layer, wherein a compound coupling agent exists between the Parylene layer and a substrate to be plated, the compound coupling agent comprises a silane coupling agent and an N-containing coupling agent, the mass ratio of the silane coupling agent to the N-containing coupling agent is 1 (0.2-3), and the compound coupling agent is respectively in chemical bonding with the Parylene layer and the substrate to be plated.
The mass ratio of the silane coupling agent to the N-containing coupling agent is 1 (0.2-3), and specifically can be, for example, 1:0.2, 1:0.3, 1:0.5, 1:0.8, 1:1, 1.0:1.2, 1:1.5, 1:1.7, 1:2.0, 1:2.3, 1:2.5, 1:2.8, 1:3.0, etc., and a range between any two point values.
The silane coupling agent is selected from gamma-aminopropyl triethoxysilane, ethyl silicate and
、、、、、、、、At least one of them or its corresponding hydrolytic condensate.
The N-containing coupling agent has the following general formula of A- (M) p-B, wherein p=0 or 1, and the mass content of N in the N-containing coupling agent is 1.5% -20%, preferably 3% -20%.
Wherein A comprises、、、、、、、、、Wherein the wavy line represents a bond to M;
b comprises 、、、、、Thiourea group,R 1 is selected from H or alkyl with 1-9 carbon atoms, R 2 is selected from H or alkyl with 1-9 carbon atoms, wherein the wavy line represents a bond with M;
M comprises 、-CO-、、、One of the above-mentioned materials is used for the preparation of the liquid,
Wherein n1 is 1-12, n2 is 1-6, n3 is 1-6;a is 1-6, b is 0-3, c is 0-3, d is 0-8.
The N-containing coupling agent A- (M) p-B of the present invention may be obtained commercially or by synthesis, and the synthesis method may be any synthesis method corresponding to the existing one with reference 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.
Exemplary N-containing coupling agents areThe preparation method can be used for preparing the composite material by the following steps:
Vinyl triethoxysilane, tetraethyl orthosilicate, hexamethyldisiloxane, acetic acid, deionized water and isopropanol are added into a reaction vessel, and the reaction solution is obtained by stirring at a certain temperature (20-30 ℃). Neutralizing 3-aminopropyl triethoxysilane with acetic acid, adding the obtained neutralization solution into the reaction solution, continuously stirring, removing solvent by rotary evaporation after the reaction, dissolving the hydrolysate in toluene, washing with deionized water, drying, and spin drying.
In some preferred embodiments of the present invention, the N-containing coupling agent is at least one of N-methyl-3-aminopropyl trimethoxysilane, N-diethylaminoethyl acrylate, di, N' -diethylacrylamide, N-methylallylamine, allylurea, methacryloylhydrazide, 4-acryloylmorpholine, diallylamine, triallylamine, allylthiourea, N-dimethylallylamine, 4-penten-1-amine, 2-aminoethyl methacrylate. The adoption of the preferable scheme matched with the silane coupling agent is beneficial to compensating the ageing resistance to a certain extent, is more beneficial to improving the adhesive force, can achieve the maximum adhesive force by further shortening the process time, and is further beneficial to improving the uniformity of all samples in a batch and the stability between batches.
In some preferred embodiments of the present invention, the N-containing coupling agent is at least one of methacryloyl hydrazide, diallyl amine, triallyl amine, N-dimethylallyl amine, 4-penten-1-amine, 2-aminoethyl methacrylate. The solution of introducing the preferable N-containing coupling agent has better catalytic performance, is mainly used for catalyzing the hydrolytic condensation reaction of the silane coupling agent, is more beneficial to improving the binding force, can lead the compound coupling agent to have proper molecular weight, volatility and corrosiveness, is more beneficial to improving the adhesive force, can achieve the maximum adhesive force by further shortening the process time, and is further beneficial to improving the uniformity of all samples in a batch and the stability between batches.
In the invention, preferably, when the silane coupling agent contains oxime groups and acetyl groups, oxime and acetic acid are released in the hydrolysis process, and the two small molecules can help the corrosion of the base material, so that the generation of mechanical strength is further promoted.
In some preferred embodiments of the present invention, the compound coupling agent is 0.5% -32% of the mass of the Parylene layer, for example, 0.5%、1.0%、1.5%、2.0%、2.5%、3.0%、3.5%、4.0%、4.5%、5.0%、5.5%、6.0%、6.5%、7.0%、7.5%、8.0%、9.0%、10.0%、11%、12%、13%、14%、15%、16%、17%、18%、19%、20%、21%、22%、23%、24%、25%、26%、27%、28%、29%、30%、31%、32%% and the like, and a range between any two point values, for example, 0.5% -6.0% may be preferred. The proper proportioning of the compound coupling agent and the Parylene can improve the total content of the Parylene in the film layer, ensure the stronger adhesive force of the Parylene and is more beneficial to the barrier property of the Parylene coating.
The adhesion force of the coupling agent in the prior art cannot be immediately improved after the adhesion is discharged, and the coupling agent and water vapor need to be reacted for 3-4 days after a curing process, so that the adhesion force can be ensured to meet the industrial requirements (for example, generally, the strength of the adhesion force is judged by using a hundred-gram method in the field, such as using A174, the adhesion force just discharged from the furnace is 2-3B, and the adhesion force can be increased to 4-5B after the coupling agent and water vapor are placed for 3-4 days).
The special compound coupling agent can realize the state that the adhesive force of the adhesive compound coupling agent is the maximum after the adhesive compound coupling agent is discharged from a furnace (for example, after the adhesive force reaches 4-5B immediately after the adhesive compound coupling agent is discharged from the furnace, and after the adhesive compound coupling agent is placed for a period of time, the adhesive force can not rise any more), which is mainly beneficial to the Michael addition reaction between N in the N-containing coupling agent and double bonds and the potential free radical chain transfer reaction, and the N-containing coupling agent can catalyze the hydrolysis reaction of the silane coupling agent, so that a plurality of possible reactions are overlapped, the integral reaction rate is accelerated, and the processing time for improving the adhesive force is shortened.
In a second aspect, the invention provides a preparation method of a Parylene coating containing a compound coupling agent, which is used for preparing the Parylene coating containing the compound coupling agent in the first aspect. And the preparation method of the Parylene coating containing the complexing agent comprises the following steps:
dissolving an N-containing coupling agent and a silane coupling agent in an alcohol solvent and water for mixing, or carrying out hydrolytic condensation on the N-containing coupling agent, the silane coupling agent and the water to obtain a solution containing a compound coupling agent;
then the substrate to be plated is soaked in the solution containing the compound coupling agent for 10-120min, then dried, and then the Parylene layer is deposited.
The specific type of the alcohol solvent in the present invention may be, for example, isopropanol, as long as it can dissolve the N-containing coupling agent and the silane coupling agent.
In some preferred embodiments of the present invention, the hydrolytic condensation conditions include a hydrolytic condensation temperature of from room temperature to 60 ℃.
Further preferably, in the hydrolytic condensation, the mass amount of water is 0.1 to 20wt% of the total amount of the N-containing coupling agent and the silane coupling agent. Wherein the degree of hydrolysis can be controlled by controlling the amount of water in the hydrolytic condensation, for example, partial hydrolysis can be achieved by making the water content smaller than the molar ratio of the siloxane-carbon bonds.
Further preferably, the hydrolytic condensation time is 0.5 to 24 hours, further preferably 1 to 24 hours, more preferably 1 to 3.5 hours.
In some preferred embodiments of the second aspect of the present invention, the mass concentration of the compounding coupling agent in the solution containing the compounding coupling agent is 0.5wt% to 9wt%, preferably 1wt% to 5wt%.
In some preferred embodiments of the second aspect of the present invention, the conditions for drying include a drying temperature of 40-100 ℃ for a period of 1-3 hours.
In a third aspect, the present invention provides a method for preparing a Parylene coating containing a compound coupling agent, which is used for preparing the Parylene coating containing a compound coupling agent in the first aspect, and the method for preparing the Parylene coating containing a compound coupling agent comprises:
dissolving an N-containing coupling agent and a silane coupling agent in an alcohol solvent and water for mixing, or carrying out hydrolytic condensation on the N-containing coupling agent, the silane coupling agent and the water to obtain a solution containing a compound coupling agent;
Then in vacuum environment, the compound coupling agent in the solution containing the compound coupling agent is controlled to volatilize, so that the volatilized compound coupling agent reacts on the surface of the substrate to be plated, and then a Parylene layer is deposited, so that the volatilized compound coupling agent and the Parylene react on the surface of the substrate to be plated.
In some preferred embodiments of the third aspect of the present invention, the conditions under which the compounded coupling agent volatilizes include a vacuum of 50-300mTorr, a temperature of 40-250℃and a time of 0.5-5 hours.
In a fourth aspect, the present invention provides a method for preparing a Parylene coating containing a compound coupling agent, which is used for preparing the Parylene coating containing a compound coupling agent in the first aspect, and the method for preparing the Parylene coating containing a compound coupling agent comprises:
dissolving an N-containing coupling agent and a silane coupling agent in an alcohol solvent and water for mixing, or carrying out hydrolytic condensation on the N-containing coupling agent, the silane coupling agent and the water to obtain a solution containing a compound coupling agent;
Placing the solution containing the compound coupling agent into an atomization chamber, volatilizing the compound coupling agent in a vacuum heating environment, and enabling the volatilized compound coupling agent to react on the surface of the substrate to be plated; and then depositing a Parylene layer, so that the compound coupling agent and the Parylene react on the surface of the substrate to be plated. The reaction of the volatile compound coupling agent in the surface reaction of the substrate to be plated comprises several layers, namely, the first layer possibly has coordination reaction with metal, the second layer slightly corrodes the metal, the third layer has permeation of small molecules, and then free radical reaction occurs again under the action of parylene.
In the third aspect and the fourth aspect of the present invention, the preparation process of the compound coupling agent is the same as that of the second aspect, and is not described herein.
In the third aspect and the fourth aspect of the present invention, the volatilization of the compound coupling agent may be performed in a vacuum environment, in which the N-containing coupling agent and the silane coupling agent are volatilized simultaneously or the N-containing coupling agent and the silane coupling agent are volatilized stepwise (for example, the silane coupling agent is volatilized first and the N-containing coupling agent is volatilized later), the N-containing coupling agent and the silane coupling agent are volatilized simultaneously or volatilized stepwise by heating and/or pressurizing the two AP devices contained in the vacuum evaporation apparatus in combination with a heating and pressurizing mechanism on the AP device, and after the volatilization, a residence time (for example, residence time of 0.5 to 3 hours) may be performed, and then the Parylene layer is deposited or the Parylene layer is directly deposited without residence. The step-by-step volatilization is preferred, namely, volatilizing one of the N-containing coupling agent and the silane coupling agent before volatilizing the other, for example, volatilizing the silane coupling agent before volatilizing the N-containing coupling agent, so that the N-containing coupling agent is ensured to be a small molecule and has better permeability. If the compound coupling agent formed by hydrolytic condensation is volatilized at the same time (such as the compound coupling agent formed by hydrolytic condensation needs to be volatilized at the same time), after the molecular weight is increased, only static adsorption is carried out in the phase change process, and no riveting force is generated, so that a certain loss is caused on the adhesion force and the adhesion reliability.
In some preferred embodiments of the fourth aspect of the present invention, the vacuum heating conditions include a vacuum degree of 50 to 300 mTorr, a temperature of 40 to 250 ℃ and a time of 0.5 to 5 hours.
The N-containing coupling agent disclosed by the invention has the advantages that the molecular weight is small, the gasification is easy (the boiling point is low), the reaction activity and the penetrating power (the reaction cannot be carried out before the penetration, or the combination is unstable, and the N-containing coupling agent and the silane coupling agent have proper catalytic activity after the penetration simultaneously), so that the adhesive force is obviously improved, meanwhile, the maximum adhesive force can be achieved only by a short process time, the good heat resistance is achieved, the uniformity of all samples in one batch is excellent, and the stability among multiple batches is excellent.
In the volatilization or atomization method, for a relatively volatile silane coupling agent such as a174, since a trimethoxysilane group is at one end of a174, the group must react with water vapor to be effective, but trimethoxysilane reacts with water relatively slowly, usually for 7 days, to achieve complete reaction. Therefore, under the condition that no N-containing coupling agent is introduced, the production efficiency is greatly reduced, the probability of contact between silane and water vapor is also reduced due to the extremely strong water blocking performance of parylene, and therefore, under the condition that no catalyst is used, the reaction time is slower, the contact probability of water vapor is lower, and the A174 is extremely difficult to take effect on a plurality of substrates to be plated. The invention adopts the N-containing coupling agent and the silane coupling agent for proper compounding, can catalyze the reaction of A174, greatly improves the production efficiency, remarkably improves the adhesive force, can achieve the maximum adhesive force with shorter process time, and has better heat resistance, excellent uniformity of all samples in one batch and excellent stability among multiple batches.
In the preparation method of the second to fourth aspects of the present invention, the mass ratio of the compound coupling agent and the Parylene layer in the obtained Parylene coating may be controlled by controlling the amount of each raw material fed.
In the second to fourth aspects of the present invention, CVD is used to deposit the Parylene layer from PARYLENE N, PARYLENE C, PARYLENE F or PARYLENE HT, and the deposition process may be performed by referring to the prior art, which is not described herein.
In a fifth aspect, the invention provides an application of the Parylene coating containing the compound coupling agent in the first aspect in surface protection of a substrate to be plated.
In some preferred embodiments of the present invention, the substrate to be plated is any one of metal, ceramic, glass. The metal may be, for example, copper, silver, gold plated, stainless steel, 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 N-containing coupling agent is N-methyl-3-aminopropyl trimethoxy silane. The mass content of N in the N-containing coupling agent is 7.24%.
The silane coupling agent is。
A Parylene coating containing a compound coupling agent is prepared by the following preparation method:
The preparation of the compound coupling agent comprises the steps of placing the N-containing coupling agent and the silane coupling agent in isopropanol, adding water, stirring and mixing for 2 hours at room temperature to obtain an isopropanol solution containing the compound coupling agent. The mass ratio of the silane coupling agent to the N-containing coupling agent is 3:1, and the mass dosage of water is 3.90 weight percent of the total amount of the N-containing coupling agent and the silane coupling agent. The mass concentration of the compound coupling agent in the isopropanol solution containing the compound coupling agent is 2.50wt%;
Then the substrate to be plated is soaked in isopropanol solution containing a compound coupling agent for 1h, and then is dried, wherein the drying condition comprises that the drying temperature is 65 ℃ and the time is 1h, and then a Parylene layer is deposited by adopting PARYLENE N as a raw material through CVD. The dosage of the compound coupling agent is 1.5 percent of the mass of the Parylene layer.
Example 2
The procedure of example 1 was carried out, except that the mass ratio of the silane coupling agent to the N-containing coupling agent was 1:1.
Example 3
The procedure of example 1 was followed, except that the N-containing coupling agent was N, N-diethylaminoethyl acrylate (commercially available from International pharmaceutical Commission Co., ltd.). The mass content of N in the N-containing coupling agent is 8.18 percent.
Example 4
The procedure of example 1 was followed, except that the N-containing coupling agent was bis (3-trimethoxysilylpropyl) amine (commercial manufacturer: national chemical reagent Co., ltd.). The N-containing coupling agent contains 4.09% by mass of N.
Example 5
The procedure of example 1 was followed except that the N-containing coupling agent was dimethylaminoethyl acrylate (commercial manufacturer: national chemical reagent Co., ltd.). The mass content of N in the N-containing coupling agent is 9.78%.
Example 6
The procedure of example 1 was followed, except that the silane coupling agent was:
(commercial manufacturers: mai Tong advanced Material group).
Example 7
The procedure of example 1 was followed, except that the silane coupling agent was:
(commercial manufacturer: national medicine group chemical reagent Co., ltd.).
Example 8
The procedure of example 1 was followed except that the silane coupling agent was vinyltributylketoxime silane (commercial manufacturer: national chemical reagent Co., ltd.).
Example 9
The procedure of example 1 was followed, except that the silane coupling agent was tris (isopropoxy) vinylsilane (commercially available manufacturer: national pharmaceutical chemicals Co., ltd.).
Example 10
The procedure of example 1 was followed except that the dosing amount of the compounded coupling agent was adjusted so that the dosing amount of the compounded coupling agent was 7% of the dosing mass of the Parylene.
Example 11
The procedure of example 1 was followed, except that after the preparation of the compounded coupling agent, the preparation method of the reaction was different, specifically as follows:
Under the vacuum environment, the vacuum degree is 250mTorr, the silane coupling agent and the N-containing coupling agent are controlled to volatilize in a step by controlling the opening and closing of two AP devices in the vacuum evaporation equipment, wherein the silane coupling agent is volatilized firstly, then the N-containing coupling agent is volatilized, the volatilization temperature is room temperature, the volatilized compound coupling agent reacts on the surface of a substrate to be plated for 2 hours, and after the reaction is stopped for 2 hours, a Parylene layer is deposited by CVD (the deposition process is the same as in the embodiment 1), so that the volatilized compound coupling agent and the Parylene react on the surface of the substrate to be plated.
Example 12
The procedure of example 1 was followed, except that the preparation process was varied as follows:
carrying out partial hydrolytic condensation (namely incomplete hydrolysis and partial alkoxy silicon functional groups are reserved) on the N-containing coupling agent and the silane coupling agent by reducing the content of added water to obtain a complex coupling agent;
Placing the solution containing the compound coupling agent into an atomization chamber, volatilizing the compound coupling agent in a vacuum heating environment at the vacuum degree of 250mTorr and the temperature of 150 ℃ for 3 hours to enable the volatilized compound coupling agent to react on the surface of the substrate to be plated, and then adopting CVD to deposit a Parylene layer (the deposition process is the same as that of the embodiment 1) to enable the compound coupling agent and the Parylene to react on the surface of the substrate to be plated.
Example 13
The process of example 1 was followed, except that in the soaking process of example 1, the key process parameters were adjusted, hydrolysis time was adjusted from 2h to 4h.
Example 14
The method of example 11 is referred to, except that the preparation of the compound coupling agent comprises the steps of carrying out hydrolytic condensation on the N-containing coupling agent, the silane coupling agent and water at 25 ℃ for 0.5h (room temperature) to form a complex coupling agent hydrolytic condensate, wherein the dosage of the N-containing coupling agent and the silane coupling agent is the same as that of example 1, and the mass dosage of the water is 10wt% of the total dosage of the N-containing coupling agent and the silane coupling agent;
In the vacuum evaporation step of example 11, the opening and closing of the two AP devices contained in the vacuum evaporation apparatus and the heating and pressurizing are used to control the hydrolysis condensate of the compound coupling agent to volatilize (which is equivalent to the simultaneous volatilization of the silane coupling agent and the N-containing coupling agent), so that the volatilized compound coupling agent reacts on the surface of the substrate to be plated for 2 hours, and after the reaction is stopped for 2 hours, the Parylene layer is deposited by CVD (the deposition process is the same as in example 1), so that the volatilized compound coupling agent and the Parylene react on the surface of the substrate to be plated.
Example 15
The process according to example 1 is carried out, with the difference that the N-containing coupling agent isThe N content was 1.87%. The N-containing coupling agent is prepared by the following preparation method:
43g of vinyltriethoxysilane (national pharmaceutical systems chemical Co., ltd.), 47.1g of tetraethylorthosilicate (national pharmaceutical systems chemical Co., ltd.), 110.0g of hexamethyldisiloxane (national pharmaceutical systems chemical Co., ltd.), 10g of acetic acid (national pharmaceutical systems chemical Co., ltd.), 40g of deionized water and 681g of isopropyl alcohol (national pharmaceutical systems chemical Co., ltd.) were charged into the three-necked flask, and stirred at 25℃for 1 hour to obtain a reaction solution. Neutralizing 3-aminopropyl triethoxysilane with 14g acetic acid, adding the obtained neutralization solution into the reaction solution, continuously stirring for 1h, removing the solvent by rotary evaporation after the reaction, dissolving the hydrolysis product in toluene, washing with deionized water for three times, drying, and spin-drying to obtain the silane coupling agent with N, vinyl and organosilicon as the framework.
Example 16
The process of example 1 is followed, except that the silane coupling agent is(Commercial manufacturer: national medicine group chemical reagent Co., ltd.).
Example 17
The process of example 1 is followed, except that the silane coupling agent is(Commercial manufacturer: national medicine group chemical reagent Co., ltd.).
Example 18
The procedure of example 1 was followed, except that the N-containing coupling agent was dimethylaminoethyl methacrylate (commercially available manufacturer: national medicine group chemical Co., ltd.) in which the N content was 8.92%.
Example 19
The process according to example 1 is carried out, with the difference that the N-containing coupling agent is(Commercial manufacturer: national medicine group chemical Co., ltd.) wherein the N content was 14.4%.
Example 20
The procedure of example 1 was followed, except that the N-containing coupling agent was 3-aminopropyl trimethoxysilane (commercially available manufacturer: national chemical reagent Co., ltd.) having an N content of 7.81%.
Example 21
The process according to example 1 is carried out, with the difference that the N-containing coupling agent is(Commercial manufacturer: nanjing medical stone technologies Co., ltd.) wherein the N content was 24.6%.
Example 22
The process according to example 1 is carried out, with the difference that the N-containing coupling agent is(Commercial manufacturer: national medicine group chemical reagent Co., ltd.) the N content was 9.03%.
Example 23
The process according to example 1 is carried out, with the difference that the N-containing coupling agent is(Commercial manufacturer: nanjing medical stone science and technology Co., ltd.) the N content was 28%.
Example 24
The process according to example 1 is carried out, with the difference that the N-containing coupling agent is(Commercial manufacturer: nanjing medical stone science and technology Co., ltd.) the N content was 7.41%.
Comparative example 1
The procedure of example 1 was followed, except that no N-containing coupling agent was added.
Comparative example 2
The procedure of example 1 was carried out, except that the silane coupling agent was not added.
Comparative example 3
The procedure of example 1 was carried out, except that the N-containing coupling agent was N-methylpiperidine (commercial manufacturer: national medicine group chemical Co., ltd.) and the N content was 14.12% by mass.
Comparative example 4
The procedure of example 1 was carried out, except that the mass ratio of the silane coupling agent to the N-containing coupling agent was 1:7.
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 tables 1,2 and 3, respectively. The binding force is tested according to a standard ASTM D3359 hundred-grid test method, the binding force grade is shown in tables 1,2 and 3, the higher the grade number is, the stronger the binding force is, the hundred-grid test method comprises scribing the surface of the coating according to the standard, then adhering the coating by using 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.
The batch stability is characterized by testing the binding force of corresponding slides (namely glass slides, stainless steel, aluminum sheets, gold-plated sheets and copper sheets) at each position of the upper part, the inner part, the middle part, the outer part, the middle part, the lower part and the outer part of the multi-batch co-plating sheet furnace. And a batch of internal uniformity indexes are used for testing the binding force characterization of corresponding slides at each position of the upper part, the outer part, the upper part, the middle part, the lower part and the outer part of the accompanying plating sheet furnace.
Table 3 (where NA represents an initial test value of 0)
Compared with the comparative example, the adhesive force can be obviously improved by adopting the embodiment of the invention, meanwhile, the maximum adhesive force can be achieved only by a short process time, and the heat resistance, the uniformity of all samples in one batch and the stability among multiple batches are good. Further, according to the embodiment 1 and the embodiments 2 to 24, the preferred specific compounding scheme of the present invention is more beneficial to improving the adhesion, and has better heat resistance, excellent uniformity of all samples in one batch, and excellent stability among multiple batches.
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.
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