CN116769375A - Self-curing protective agent composition - Google Patents
Self-curing protective agent composition Download PDFInfo
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- CN116769375A CN116769375A CN202310830703.6A CN202310830703A CN116769375A CN 116769375 A CN116769375 A CN 116769375A CN 202310830703 A CN202310830703 A CN 202310830703A CN 116769375 A CN116769375 A CN 116769375A
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- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 239000003223 protective agent Substances 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 68
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 55
- 239000011737 fluorine Substances 0.000 claims abstract description 55
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 18
- 150000003254 radicals Chemical class 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- -1 acrylic ester Chemical class 0.000 claims description 25
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 claims description 9
- 150000008282 halocarbons Chemical group 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 7
- PHPRWKJDGHSJMI-UHFFFAOYSA-N 1-adamantyl prop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C=C)C3 PHPRWKJDGHSJMI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010702 perfluoropolyether Chemical group 0.000 claims description 4
- WVXMNBDPVYOPLX-UHFFFAOYSA-N 2-isocyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCC[N+]#[C-] WVXMNBDPVYOPLX-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011253 protective coating Substances 0.000 abstract description 8
- 230000003373 anti-fouling effect Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 description 21
- 239000010408 film Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
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- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- 229920002313 fluoropolymer Polymers 0.000 description 8
- 239000004811 fluoropolymer Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NOPJRYAFUXTDLX-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane Chemical compound COC(F)(F)C(F)(F)C(F)(F)F NOPJRYAFUXTDLX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
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- CWIFAKBLLXGZIC-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane Chemical compound FC(F)C(F)(F)OCC(F)(F)F CWIFAKBLLXGZIC-UHFFFAOYSA-N 0.000 description 1
- YQQHEHMVPLLOKE-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-methoxyethane Chemical compound COC(F)(F)C(F)F YQQHEHMVPLLOKE-UHFFFAOYSA-N 0.000 description 1
- PBVZTJDHQVIHFR-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F PBVZTJDHQVIHFR-UHFFFAOYSA-N 0.000 description 1
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 1
- SQEGLLMNIBLLNQ-UHFFFAOYSA-N 1-ethoxy-1,1,2,3,3,3-hexafluoro-2-(trifluoromethyl)propane Chemical compound CCOC(F)(F)C(F)(C(F)(F)F)C(F)(F)F SQEGLLMNIBLLNQ-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
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- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a self-curing protective agent composition, which consists of a self-curing fluorine-containing polymer and a fluorine-containing solvent, wherein the self-curing fluorine-containing polymer is prepared by free radical copolymerization of at least fluorine-containing acrylate monomers, non-fluorine-containing acrylate monomers containing cyclic groups or tert-butyl groups and acrylate monomers containing isocyanate groups. The self-curing protective agent composition can form a protective coating film with excellent durable waterproof and antifouling performance and excellent antirust performance on the surface of an electronic device, and does not influence the original service performance of the electronic device.
Description
Technical Field
The invention relates to a self-curing protective agent composition, belongs to the technical field of surface protection, and particularly relates to surface protection of electronic components.
Background
The sputtered metal or metal oxide coating on the surface of the electronic device can prevent micro cracks or gaps possibly formed in the use process of the electronic device, thereby preventing malfunction caused by abnormal current flow. However, the sputtered layer is porous and has high surface energy, and is easy to be polluted by dirt or rusted, so that the required performance of the coating is adversely affected. Therefore, it is important to perform surface protection treatment on the sputtered layer. The resin coating is a common method, but the conventional resin coating is required to be cured, has low efficiency and is easy to generate defects, and is not suitable for miniaturized electronic components.
The fluoropolymer can impart a protective effect to a substrate at a relatively thin film thickness (1 μm or less). The protective coating film can be formed by applying a solution of a fluoropolymer dissolved in a nonflammable low boiling point solvent to the surface of the electronic component and drying the solvent. However, existing fluoropolymer protectants are difficult to combine in terms of durable stain resistance and rust resistance.
Disclosure of Invention
The invention aims to provide a self-curing protective agent composition, which can form a protective coating film with excellent durable waterproof and antifouling performance and excellent antirust performance on the surface of an electronic device, and does not influence the original service performance of the electronic device.
In order to achieve the purpose of the invention, the following technical scheme is adopted:
a self-curing protective agent composition consists of self-curing fluorine-containing polymer and fluorine-containing solvent; the self-curing fluorine-containing polymer at least comprises fluorine-containing acrylic ester monomer units, non-fluorine-containing acrylic ester monomer units containing cyclic groups or tert-butyl groups and acrylic ester monomer units containing isocyanate groups; the self-curing fluorine-containing polymer is prepared by free radical copolymerization of at least fluorine-containing acrylic ester monomers, non-fluorine-containing acrylic ester monomers containing cyclic groups or tert-butyl groups and acrylic ester monomers containing isocyanate groups.
Further, the self-curing fluoropolymer contains at least 3 parts by weight of an acrylate monomer unit containing an isocyanate group and at most 25 parts by weight of a non-fluorinated acrylate monomer unit containing a cyclic group or a t-butyl group, based on 100 parts by weight of the self-curing fluoropolymer.
Further, the fluorine-containing acrylic ester monomer is represented by the general formula CH 2 ＝C(R)COO-Z-R f Wherein R is H, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, Z is a divalent organic group, and Rf is a polyfluoroalkyl group or a polyfluoropolyether group.
Furthermore, the fluorine-containing acrylic ester monomer is represented by the general formula CH 2 ＝C(R)COO-Z-R f Wherein R is H, a halogen atom, a hydrocarbonA radical, a halogenated hydrocarbon radical, Z is a divalent organic radical, R f Represents a perfluoroalkyl group having 4 to 8 carbon atoms or a perfluoropolyether group having a molecular weight of 300 or more.
In the further step, the fluorine-containing acrylic ester monomer is CH 2 ＝C(CH 3 )COOCH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 Or CH (CH) 2 ＝CHCOOCH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 One of them.
Further, the non-fluorinated acrylate monomer containing a cyclic group or a tert-butyl group is at least one of cyclic alkyl acrylate, cyclic alkyl methacrylate, tert-butyl acrylate and tert-butyl methacrylate.
Further, the non-fluorine-containing acrylic monomer containing a cyclic group or a tert-butyl group is one of adamantyl acrylate or tert-butyl methacrylate.
Further, the acrylate monomer containing isocyanate group is represented by the general formula CH 2 And C (R ') COO-Q-NCO, wherein R' is H, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, and Q is a divalent organic group.
Further, the acrylate monomer containing isocyanate groups is one of isocyanatoethyl methacrylate or isocyanatoethyl acrylate.
Further, the fluorine-containing solvent at least comprises a hydrofluoroether solvent.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the protective coating formed by the self-curing protective agent composition can endow a substrate with excellent durable waterproof and antifouling performance and excellent antirust performance, and the original service performance of an electronic device is not affected; the protective agent composition can be self-cured to form a film, so that the wear resistance is excellent; the composition is composed of self-curing fluorine-containing polymer and fluorine-containing solvent, and the fluorine-containing solvent does not generate solvent corrosion to the substrate.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, and to provide a preferred embodiment of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The self-curing protective agent composition of the invention consists of self-curing fluorine-containing polymer and fluorine-containing solvent. The self-curing fluoropolymer is an active ingredient of the composition, and after being applied to the surface of a substrate (especially an electronic component), an extremely thin curing protective film is formed, which can impart excellent durable water-proof and stain-proof properties and excellent rust-proof properties to the substrate. The self-curing fluorine-containing acrylate monomer unit in the self-curing fluorine-containing polymer is an essential component for providing a water-repellent and stain-proofing function, and the isocyanate group-containing acrylate monomer unit is an essential component for providing a self-curing function, both of which are indispensable. Although the acrylate monomer unit containing alkoxysilane can also provide a self-crosslinking function, the protective film formed when copolymerized with the monomer has almost no rust inhibitive performance. The non-fluorinated acrylate monomer unit containing a cyclic group or a tert-butyl group in the self-curable fluoropolymer is not clear in functional properties, but is still indispensable, and has an auxiliary synergistic effect, otherwise the protective performance of the formed protective coating may be lowered.
The self-curing fluoropolymer of the present invention has too little acrylate monomer unit containing isocyanate groups, and the protective coating has unsatisfactory wear resistance and high and low temperature impact resistance. Therefore, it is preferable that the self-curable fluorine-containing polymer contains at least 3 parts by weight of an acrylate monomer unit containing an isocyanate group based on 100 parts by weight. However, too high an amount is not recommended, and the protective coating film performance after the increase of the amount is substantially stable, but the increase of the amount is disadvantageous for the stability of the product, so that the amount is more preferably 3 to 12 parts.
The non-fluorinated acrylate monomer unit containing the cyclic group or the tert-butyl group in the self-curing type fluorine-containing polymer has an auxiliary synergy effect, but the dosage is not excessively high, otherwise, the protective coating film can be adversely affected. Therefore, it is preferable that the self-curable fluorine-containing polymer contains at most 25 parts by weight of a non-fluorinated acrylate monomer unit containing a cyclic group or a t-butyl group, based on 100 parts by weight of the self-curable fluorine-containing polymer.
General formula CH for fluorine-containing acrylic ester monomer 2 ＝C(R)COO-Z-R f Wherein R is H, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, Z is a divalent organic group, R f Is a polyfluoroalkyl group or a polyfluoropolyether group. Halogen atoms, e.g. fluorine, chlorine, bromine, hydrocarbon radicals, e.g. C 1～10 Alkyl, cycloalkyl, phenyl, benzyl, etc., haloalkyl such as trifluoromethane, etc. Divalent organic groups such as (CH) 2 ) n (n is an integer of 1 to 6), CH 2 CH 2 N(CH 3 )SO 2 、CH 2 CH 2 N(CH 2 CH 3 )SO 2 、CH(CH 3 )CH 2 N(CH 3 )SO 2 、CH 2 CH 2 NH、N(CH 3 )CH 2 CH 2 NH, and the like. Polyfluoroalkyl groups such as (CF) 2 ) 2 CF 3 、CF(CF 3 ) 2 、(CF 2 ) 3 CF 3 、CF 2 CF(CF 3 ) 2 、C(CF 3 ) 3 、(CF 2 ) 4 H、(CF 2 ) 2 CF(CF 3 ) 2 、(CF 2 ) 5 CF 3 、(CF 2 ) 7 CF 3 Etc.; polyfluoropolyether groups such as CF (CF) 3 )[OCF 2 CF(CF 3 )] p OCF 2 CF 2 CF 3 、CF 2 [OCF 2 CF 2 ] p OCF 3 、C(O)CF(CF 3 )(OCF 2 CF(CF 3 )) p OC 3 F 7 、C(O)CF(OCF 2 CF 2 ) p OCF 3 The average value of p is 1 to 30.
Preferably, the fluoroacrylate monomer is represented by the general formula CH 2 ＝C(R)COO-Z-R f Wherein R is H, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, Z is a divalent organic group, R f Represents a perfluoroalkyl group having 4 to 8 carbon atoms or a perfluoropolyether group having a molecular weight of 300 or more. Such fluoroester monomers can be exemplified as follows: CH (CH) 2 ＝CHCOOCH 2 CH 2 CF 2 CF 2 CF 2 CF 3 、CH 2 ＝C(CH 3 )COOCH 2 CH 2 CF 2 CF 2 CF 2 CF 3 、CH 2 ＝CHCOOCH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 、CH 2 ＝C(CH 3 )COOCH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 、CH 2 ＝CHCOOCH 2 CH 2 N(CH 3 )SO 2 CF 2 CF 2 CF 2 CF 3 、CH 2 ＝C(CH 3 )COOCH 2 CH 2 N(CH 3 )SO 2 CF 2 CF 2 CF 2 CF 3 、CH 2 ＝CHCOOCH 2 CH 2 N(CH 3 )SO 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 、CH 2 ＝C(CH 3 )COOCH 2 CH 2 N(CH 3 )SO 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 、CH 2 ＝C(CH 3 )COOCH 2 CH 2 N(CH 2 CH 3 )SO 2 CF 2 CF 2 CF 2 CF 3 、CH 2 ＝CHCOOCH 2 PFPE、CH 2 ＝C(CH 3 )COOCH 2 PFPE, wherein PFPE is a perfluoropolyether group having a molecular weight of 300 or more.
More preferably, the fluorine-containing acrylic ester monomer is CH 2 ＝C(CH 3 )COOCH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 Or CH (CH) 2 ＝CHCOOCH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 One of them.
The non-fluorinated acrylate monomer containing a cyclic group or a tert-butyl group may be exemplified as follows: at least one of tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, methylcyclopentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, derivatives having a substituent on the ring of the above-mentioned monomers, and the like.
Preferably, the non-fluorinated acrylate monomer containing a cyclic group or a tert-butyl group is at least one of cyclic alkyl acrylate, cyclic alkyl methacrylate, tert-butyl acrylate and tert-butyl methacrylate.
More preferably, the non-fluorinated acrylate monomer containing a cyclic group or a tert-butyl group is one of adamantyl acrylate or tert-butyl methacrylate.
The acrylate monomer containing isocyanate groups is a monomer containing both acrylate double bonds and isocyanate groups.
Preferably, the acrylate monomer containing isocyanate groups is of the formula CH 2 And C (R ') COO-Q-NCO, wherein R' is H, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, and Q is a divalent organic group.
More preferably, the acrylate monomer containing isocyanate groups is one of isocyanoethyl methacrylate or isocyanoethyl acrylate.
The self-curing protective agent composition of the invention comprises a self-curing fluorine-containing polymer and a fluorine-containing solvent, wherein the fluorine-containing solvent at least comprises a hydrofluoroether solvent. The hydrofluoroether is an ether in which a part of hydrogen atoms is replaced with fluorine atoms, and the following can be mentioned: nonafluorobutyl methyl ether (CF) 3 CF 2 CF 2 CF 2 OCH 3 ) Nonafluoroisobutyl methyl ether ((CF) 3 ) 2 CFCF 2 OCH 3 ) Nonafluorobutyl ether (CF) 3 CF 2 CF 2 CF 2 OCH 2 CH 3 ) Nonafluoroisobutyl ether ((CF) 3 ) 2 CFCF 2 OCH 2 CH 3 )、HFE-254(CH 3 OCF 2 CF 2 H)、HFE-347(CF 3 CH 2 OCF 2 CF 2 H)、HFE-374(CH 3 CH 2 OCF 2 CF 2 H)、HFE-494n(CH 3 CH 2 CH 2 OCF 2 CF 2 H)、HFE-494i((CH 3 ) 2 CHOCF 2 CF 2 H)、HFE-494e2(CH 3 OCH 2 CH 2 OCF 2 CF 2 H)、HFE-5114n(CH 3 (CH 2 ) 3 OCF 2 CF 2 H)、HFE5114i((CH 3 ) 2 CHCH 2 OCF 2 CF 2 H)、HFE-894m(m-CH 3 C 6 H 4 OCF 2 CF 2 H)、HFE-894Bz(C 6 H 5 CH 2 OCF 2 CF 2 H)、HFE-458(HCF 2 CF 2 CH 2 OCF 2 CF 2 H) Etc. The 3M produced hydrofluoroether 7100 is a mixture of nonafluorobutyl methyl ether and nonafluoroisobutyl methyl ether and the 3M produced hydrofluoroether 7200 is a mixture of nonafluorobutyl ethyl ether and nonafluoroisobutyl ethyl ether. Preferably, the hydrofluoroether solvent is one of HFE-347 or 7200.
The fluorine-containing solvent may contain other fluorine solvents such as perfluorocyclic ether, hexafluoropropylene dimer, hexafluoropropylene trimer, etc., in addition to the hydrofluoroether solvent.
The self-curable fluorine-containing polymer in the self-curable protective agent composition of the present invention is obtained by radical solution polymerization of at least a fluorine-containing acrylate monomer, a non-fluorine-containing acrylate monomer containing a cyclic group or a tert-butyl group, and an acrylate monomer containing an isocyanate group. The polymerization needs a free radical initiator to initiate the polymer, and a hydrofluoroether solvent is used as a polymerization medium.
As the polymerization initiator, a usual radical initiator may be used, and oil-soluble is preferable, and for example, azo-type azobisisobutyronitrile, azobisisoheptonitrile, etc., or benzoyl peroxide, t-butyl benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, etc., may be used, but is not limited thereto. These initiators may be used alone or in combination of two or more. The amount of the initiator is not particularly limited, but the initiator is usually used in an amount of 0.02 to 5 parts by mass, preferably 0.3 to 2.5 parts by mass, more preferably 0.5 to 1.5 parts by mass, based on 100 parts by mass of the monomer and the initiator.
The polymerization system preferably employs hydrofluoroether directly as the polymerization solvent, avoiding the need for a step of evaporating the solvent after polymerization and then replacing it with the hydrofluoroether solvent. The concentration of the monomer in the polymerization system is preferably 8wt% to 60wt%, more preferably 20wt% to 50wt%, and most preferably 40wt%.
The polymerization temperature, polymerization time and the like can be appropriately adjusted according to the boiling point of the solvent, the kind of the initiator, the kind of the monomer and the like, and the polymerization temperature is usually controlled to be 50-100 ℃ and the polymerization time is controlled to be 4-24 h. The feeding mode can be selected according to the reactivity ratio of the selected comonomer, such as one-time feeding, batch feeding, continuous dripping and the like.
The concentration of the self-curable fluorine-containing polymer in the self-curable protective agent composition of the present invention is not particularly limited, and the mass concentration is preferably 2% to 35%, more preferably 8% to 15%, based on the saturated concentration.
The self-curing type protective agent composition of the present invention is not particularly limited to the treated substrate, and is applicable to metal substrates, plastic substrates, glass substrates, ceramic substrates, and the like, and a permanently cured coating film having excellent water-repellent properties can be obtained on the surface of the treated substrate. However, the self-curing type protective agent composition of the present invention is particularly suitable for the waterproofing treatment of electronic devices, and particularly suitable for the waterproofing treatment of electronic device parts, printed circuit boards, etc. which are likely to fail after encountering water, or electronic parts which are likely to be corroded in the environment to affect performance, and for electronic parts which are required to provide durable waterproofing.
By adopting the self-curing protective agent composition, after surface treatment is carried out on electronic devices and the like, the adhesion or invasion of water can be effectively inhibited, and the adhered water can be conveniently removed through proper drying treatment, so that the possible faults caused by contact with water are greatly reduced.
The method of treating the substrate with the self-curable protectant composition of the invention is not particularly limited, as long as the composition of the invention is brought into sufficient contact with the substrate to be treated, and the treatment may be carried out by dipping, spraying, brush coating, towel dipping, spin coating, or the like. The fluorinated composition for a curable waterproof coating is usually diluted to a concentration of 0.05 to 10wt%, more preferably to a concentration of 0.2 to 4wt%, depending on the substrate to be treated.
In the case of performing the surface treatment, the treatment temperature is not particularly limited, and may be usually room temperature. When dipping is adopted, the dipping time is selected according to the use requirements of different devices, and is usually between 1 second and 10 hours. When spraying is employed, the spraying speed and the number of times are also not particularly limited, and generally, it is preferable to ensure that a uniform coating film can be formed. The treated substrate is dried at room temperature under the atmosphere, but the effect is better if it is cured at 60-180 ℃ for 5-120 minutes.
In order to ensure the effect of the coating film and the durability of the coating film, the substrate is preferably cleaned to remove oil stains, impurities, and the like from the surface before the substrate is treated with the self-curing type repellent composition of the present invention. The cleaning can be acetone, isopropanol, hydrofluoroether or hydrofluorocarbon. In addition, the substrate may be optionally pretreated with plasma, corona, or the like.
The raw materials used in the invention can be purchased commercially, and are specifically as follows:
monomer C 6-M ：CH 2 ＝C(CH 3 )COOCH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 (purchased from Fujian Sannong New Material Limited liability Co.)
Monomer C 6 ：CH 2 ＝CHCOOCH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 (purchased from Fujian Sannong New Material Limited liability Co.)
Monomer A1: tert-butyl methacrylate (available from Shanghai Yongzheng chemical Co., ltd.)
Monomer A2: adamantyl acrylate (available from Wuhans microphone biotechnology Co., ltd.)
Monomeric NCO M : isocyanoethyl methacrylate (from Hubei Jiachu biological medicine Co., ltd.)
Monomeric NCO: isocyanoethyl acrylate (available from Hubei Jiachu biological medicine Co., ltd.)
Monomer Si: gamma-methacryloxypropyl trimethoxysilane (Nanjing Netherlands New Material technologies Co., ltd.)
And (3) an initiator: azodi-hexacyanophenyl (available from Shanghai Haoha chemical Co., ltd.)
Hydrofluoroethers: HFE-347 (available from Shandong Hua fluoride Co., ltd.)
Hydrofluoroethers: 7200 (purchased from 3M company, USA)
Perfluorinated solvents: hexafluoropropylene trimer (available from Zhejiang Nora fluorine chemical Co., ltd.)
Example 1
Into a 500ml three-necked flask, 84g of monomer C was charged 6-M 10g of monomer A1, 5g of monomer NCO M 1g of initiator and 150g of HFE-347, and carrying out reflux reaction for 16h in a constant temperature oil bath pot under the stirring of a magnet, thus obtaining the inventionSelf-curing protectant compositions.
Examples 2 to 12 and comparative examples 1 to 3
The same process as in example 1 was used and the specific formulation is shown in Table 1.
Table 1 formulation table
Comparative example 4
Into a 500ml three-necked flask, 80g of monomer C was charged 6-M 10g of monomer A1, 9g of monomer Si, 1g of initiator and 150g of HFE-347 are subjected to reflux reaction in a constant temperature oil bath for 16 hours under the stirring of a magnet, so as to obtain the siloxane self-curing protective agent composition.
Substrate processing method
The substrate was first cleaned with ethanol and then with HFE-347 to complete the pretreatment.
The self-curing type protectant compositions obtained in examples 1 to 12 and comparative examples 1 to 4 were diluted with hexafluoropropylene trimer to a concentration of 0.2wt% and sprayed on the surface of the pretreated substrate, and then dried at room temperature for 10 minutes, and then placed in an oven at 80℃for curing for 30 minutes to obtain test pieces.
Performance testing
(1) Contact angle test
The contact angle of the deionized water (W) and the white mineral oil (O) is tested by a contact angle tester. The measurements were performed in duplicate 5 times and averaged. The results are detailed in Table 2.
(2) Abrasion resistance test
After the contact angle with water was measured with respect to the treated sample, the sample was placed on a tribometer, surface friction was performed a prescribed number of times with a load of 100g, after which the contact angle with water was again measured, and the percentage with respect to the initial contact angle was calculated, whereby the wear resistance was evaluated. The results are detailed in Table 2.
Table 2 contact angle and abrasion resistance test
(3) Salt spray resistance test
Salt spray resistance test is carried out on the treated base material by referring to GB/T2423.17-2008, and specific test conditions are as follows: the spray liquid adopts 5% sodium chloride solution, the PH value is between 6.5 and 7.2, and the spray liquid is controlled at 35 ℃. The results are detailed in Table 3.
Table 3 salt spray resistance test
Note that: failure to obtain contact angle data after rusting
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to achieve substantially the same technical effects are included in the scope of the present invention.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description. The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A self-curing protective agent composition is composed of self-curing fluorine-containing polymer and fluorine-containing solvent, and is characterized in that:
the self-curing fluorine-containing polymer is prepared by free radical copolymerization of at least fluorine-containing acrylic ester monomers, non-fluorine-containing acrylic ester monomers containing cyclic groups or tert-butyl groups and acrylic ester monomers containing isocyanate groups.
2. The self-curing protectant composition according to claim 1, characterized in that: 100 parts by weight of the self-curing fluorine-containing polymer comprises at least 3 parts of acrylate monomer units containing isocyanate groups and at most 25 parts of non-fluorine-containing acrylate monomer units containing cyclic groups or tert-butyl groups.
3. The self-curing protectant composition according to claim 1 or 2, characterized in that: the general formula CH for the fluorine-containing acrylic ester monomer 2 ＝C(R)COO-Z-R f Wherein R is H, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, Z is a divalent organic group, R f Is a polyfluoroalkyl group or a polyfluoropolyether group.
4. A self-curing protectant composition according to claim 3, characterized in that: the general formula CH for the fluorine-containing acrylic ester monomer 2 ＝C(R)COO-Z-R f Wherein R is H, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, Z is a divalent organic group, R f Represents a perfluoroalkyl group having 4 to 8 carbon atoms or a perfluoropolyether group having a molecular weight of 300 or more.
5. The self-curing protectant composition according to claim 4, characterized in that: the fluorine-containing acrylic ester monomer is CH 2 ＝C(CH 3 )COOCH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 Or CH (CH) 2 ＝CHCOOCH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 One of them.
6. The self-curing protectant composition according to claim 1 or 2, characterized in that: the non-fluorine-containing acrylic ester monomer containing the cyclic group or the tert-butyl group is at least one of cyclic alkyl acrylate, cyclic alkyl methacrylate, tert-butyl acrylate and tert-butyl methacrylate.
7. The self-curing protectant composition according to claim 6, characterized in that: the non-fluorine-containing acrylic ester monomer containing the cyclic group or the tert-butyl group is one of adamantyl acrylate or tert-butyl methacrylate.
8. The self-curing protectant composition according to claim 1 or 2, characterized in that: the acrylate monomer containing isocyanate group is represented by a general formula CH 2 And C (R ') COO-Q-NCO, wherein R' is H, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, and Q is a divalent organic group.
9. The self-curing protectant composition according to claim 8, characterized in that: the acrylic ester monomer containing isocyanate groups is one of isocyanoethyl methacrylate or isocyanoethyl acrylate.
10. The self-curing protectant composition according to claim 1, characterized in that: the fluorine-containing solvent at least comprises a hydrofluoroether solvent.
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| CN112011010A (en) * | 2020-09-08 | 2020-12-01 | 浙江辉凯鼎瑞新材料有限公司 | Low-temperature type waterproof and oil-proof agent and preparation method and application thereof |
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| JP2005054020A (en) * | 2003-08-01 | 2005-03-03 | Yunimatekku Kk | Water and oil repellant |
| CN1938343A (en) * | 2004-03-26 | 2007-03-28 | 大金工业株式会社 | Fluorine-containing monomer, fluorine-containing polymer and surface treating agent |
| US20160237614A1 (en) * | 2013-10-23 | 2016-08-18 | Daikin Industries, Ltd. | Fluorine-containing polymer and treatment agent |
| US20160251468A1 (en) * | 2013-11-01 | 2016-09-01 | Unimatec Co., Ltd. | Fluorine-containing polymer and surface-modifying agent containing the same as active ingredient |
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