CN117343620A - Smooth anti-fingerprint liquid and preparation method thereof - Google Patents
Smooth anti-fingerprint liquid and preparation method thereof Download PDFInfo
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- 230000003666 anti-fingerprint Effects 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 30
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 82
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- -1 polyfluorosiloxane Polymers 0.000 claims abstract description 25
- 239000003085 diluting agent Substances 0.000 claims abstract description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 20
- 239000011737 fluorine Substances 0.000 claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 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 claims description 9
- 229960004624 perflexane Drugs 0.000 claims description 8
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- FNUBKINEQIEODM-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoropentanal Chemical compound FC(F)(F)C(F)(F)C(F)(F)CC=O FNUBKINEQIEODM-UHFFFAOYSA-N 0.000 claims description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 3
- 229960004692 perflenapent Drugs 0.000 claims description 3
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 claims description 3
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 claims description 3
- NJCBUSHGCBERSK-UHFFFAOYSA-N perfluoropentane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F NJCBUSHGCBERSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000013638 trimer Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 8
- 125000003709 fluoroalkyl group Chemical group 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- 229920001774 Perfluoroether Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006116 anti-fingerprint coating Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 238000010944 pre-mature reactiony Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000002268 wool Anatomy 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The application relates to the technical field of anti-fingerprint materials, and particularly provides a smooth anti-fingerprint liquid and a preparation method thereof. The slipping fingerprint resisting liquid consists of 99-99.999 wt% of fluorine-containing diluent and 0.001-1 wt% of main agent; the main agent is prepared from perfluoropolyether silane coupling agent and Me 3 SiO(SiOMeR f ) a (SiOMeR 1 ) b (SiOMeR 2 ) c SiMe 3 The polyfluorosiloxane of (2) is composed of 5-100:1 by weight ratio, wherein R is as follows f Represents a perfluoropolyether segment or a C8-C20 perfluoroalkyl segment, R 1 Selected from C1-C12 alkyl, chloro-substituted C3-C6 alkyl or C6-C12 aryl, R 2 Is of the structure-CH 2 CH 2 Si(OR 3 ) 3 ，R 3 Selected from methyl or ethyl, me represents methyl, a=10-100, b=3-10, c=3-8.The anti-fingerprint liquid has good slipping performance after film formation on glass and other base materials, and has little influence on anti-fingerprint performance and wear resistance.
Description
Technical Field
The application relates to the technical field of anti-fingerprint materials, in particular to a smooth anti-fingerprint liquid and a preparation method thereof.
Background
In order to improve the fingerprint resistance and the stain resistance of materials such as glass, a layer of nano-scale film is usually applied by spraying fingerprint resistant liquid and the like. The anti-fingerprint liquid is generally prepared by taking a long-chain fluoroalkyl silane coupling agent or a perfluoropolyether silane coupling agent as a main agent and adopting a fluorine diluent for dilution. The biggest application of the anti-fingerprint liquid is a mobile phone glass screen, a mobile phone glass film, a tablet personal computer glass screen and the like. The main index properties of the anti-fingerprint liquid are as follows: (1) Extremely low surface tension, good hydrophobic and oleophobic effects and fingerprint contamination resistance; (2) good wear resistance and durable fingerprint resistance; (3) low dynamic friction coefficient, high smoothness, etc.
The prior art discloses structures of various long-chain fluoroalkyl silane coupling agents or perfluoropolyether silane coupling agents, mainly the structures of the long-chain fluoroalkyl groups or the perfluoropolyether groups are adjusted to realize better performances of fingerprint resistance, smoothness and the like, and the modification mode is to introduce two or more alkoxy silicon-based structures into one long-chain fluoroalkyl silane coupling agent or the perfluoropolyether silane coupling agent to improve the adhesion to glass and other substrates.
In theory, when the long-chain fluoroalkyl silane coupling agent or the perfluoropolyether silane coupling agent is hydrolyzed and condensed on the surface of a substrate such as glass, three alkoxy groups are hydrolyzed, one alkoxy group is connected with the substrate, and the remaining two alkoxy groups are respectively condensed with adjacent alkoxy groups, so that a nano-scale film with the thickness of a monolayer is formed, but in practice, the nano-scale film is difficult to realize, and the performances such as fingerprint resistance, wear resistance and slipping are poor.
The inventors found that various anti-fingerprint liquids are reported in the prior art, but the anti-fingerprint performance is mainly concerned, and the smoothness is less concerned.
Disclosure of Invention
In order to solve the technical problem of insufficient smoothness performance of anti-fingerprint liquid in the prior art, the application provides a smooth anti-fingerprint liquid and a preparation method thereof.
The application adopts the following technical scheme:
a smooth fingerprint-resistant liquid consists of 99-99.999% fluorine-containing diluent and 0.001-1% main agent according to 100% by weight;
the main agent consists of a perfluoropolyether silane coupling agent and polyfluorosiloxane shown in the following formula (1) according to the weight ratio of 5-100:1,
Me 3 SiO(SiOMeR f ) a (SiOMeR 1 ) b (SiOMeR 2 ) c SiMe 3 (1)
wherein R is f Represents a perfluoropolyether segment or a C8-C20 perfluoroalkyl segment, R 1 Selected from C1-C12 alkyl, chloro-substituted C3-C6 alkyl or C6-C12 aryl, R 2 Is of the structure-CH 2 CH 2 Si(OR 3 ) 3 ，R 3 Selected from methyl or ethyl, me represents methyl, a=10-100, b=3-10, c=3-8.
Preferably, the fluorine-containing diluent is selected from one or a combination of more of perfluorohexane, perfluoroheptane, perfluorooctane, hexafluoropropylene trimer, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, perfluoropentane, perfluorohexane, ethyl perfluorobutyl ether and ethyl nonafluorobutyl ether.
Preferably, the perfluoropolyether silane coupling agent is selected from PFPECH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 、PFPECH 2 OCH 2 CH 2 CH[CH 2 CH 2 Si(OCH 3 ) 3 ] 2 、PFPECH 2 OCH[CH 2 CH 2 Si(OCH 3 ) 3 ] 2 Or PFPECH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 Wherein PFPE represents a perfluoropolyether segment.
Preferably, the weight ratio of the perfluoropolyether silane coupling agent to the polyfluoropolysiloxane is 10-100:1.
Preferably, the structure of the perfluoropolyether segment is selected from one of a D-type perfluoropolyether segment, a Z-type perfluoropolyether segment, a K-type perfluoropolyether segment and a Y-type perfluoropolyether segment.
Preferably, the C8-C20 perfluoroalkyl segment has the structure CF 3 (CF 2 ) n CH 2 CH 2 -，n＝5-17。
Preferably, the values of a, b, c satisfy: a/(a+b+c) is more than or equal to 0.7 and less than or equal to 0.9.
Preferably, the values of a, b, c satisfy: b/(a+b+c) is less than or equal to 0.05 and less than or equal to 0.2.
Preferably, the values of a, b, c satisfy: c/(a+b+c) is less than or equal to 0.03 and less than or equal to 0.1.
The preparation method of the smooth anti-fingerprint liquid according to any one of the technical schemes comprises the steps of adding the perfluoropolyether silane coupling agent and the polyfluoropolysiloxane into the fluorine-containing diluent, and uniformly stirring and mixing;
or,
and adding the perfluoropolyether silane coupling agent and the polyfluoropolysiloxane into part of the fluorine-containing diluent, uniformly mixing, and uniformly mixing with the rest of the fluorine-containing diluent before use.
In summary, the present application has the following beneficial effects:
1. polysiloxanes have better slip properties than perfluoropolyethers, but have poorer fingerprint resistance than perfluoropolyethers. According to the application, the polyfluoro siloxane is added into the anti-fingerprint liquid, and the obtained anti-fingerprint liquid has good anti-fingerprint performance, slipping performance and wear resistance through the design of the polyfluoro siloxane structure.
2. The polyfluoropolysiloxane structure comprises a fluoroalkyl structure or a fluoroether structure, an organic group and an alkoxy silicon group, wherein the fluoroalkyl structure or the fluoroether structure can provide a good compatilizer and anti-fingerprint performance for the perfluoropolyether silane coupling agent, the organic group can provide good slipping performance, and the alkoxy silicon group can provide good binding force with a substrate. Therefore, the smooth anti-fingerprint liquid has better anti-fingerprint performance and has little influence on wear resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, 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. In case of conflict, the present specification will control.
In one aspect, the application provides a smooth anti-fingerprint liquid, which consists of 99-99.999% of fluorine-containing diluent and 0.001-1% of main agent by weight of 100%;
the main agent consists of perfluoropolyether silane coupling agent and polyfluorosiloxane shown in the following formula (1) according to the weight ratio of 5-100:1,
Me 3 SiO(SiOMeR f ) a (SiOMeR 1 ) b (SiOMeR 2 ) c SiMe 3 (1)
wherein R is f Represents a perfluoropolyether segment or a C8-C20 perfluoroalkyl segment, R 1 Selected from C1-C12 alkyl, chloro-substituted C3-C6 alkyl or C6-C12 aryl, R 2 Is of the structure-CH 2 CH 2 Si(OR 3 ) 3 ，R 3 Selected from methyl or ethyl, me represents methyl, a=10-100, b=3-10, c=3-8.
In the prior art, the main agent of the anti-fingerprint liquid (the component which plays the anti-fingerprint function of the components remained after the volatilization of the diluent) generally contains the perfluoropolyether silane coupling agent, but the slipping property of the anti-fingerprint coating is insufficient due to the insufficient slipping property of the perfluoropolyether structure. Polysiloxane has better slip properties than perfluoropolyether, but direct addition of polysiloxane to anti-fingerprint liquid results in deterioration of anti-fingerprint properties, abrasion resistance, etc. The application designs polysiloxane structure, and the side chain is introduced with the perfluoropolyether chain segment and the alkoxy silicon group, the perfluoropolyether chain segment provides compatibility and fingerprint resistance with the perfluoropolyether silane coupling agent, and the alkoxy silicon group provides good binding force with a base material, so that the fingerprint resistant liquid has better slipping property and better wear resistance while maintaining better fingerprint resistant performance.
In the present application, the polyfluorosiloxane represented by formula (1) may be a mixture of hydrogen-containing silicone oil Me 3 SiO(SiOMeH) a+b+c SiMe 3 Respectively with R f Corresponding perfluoropolyether alkenyl, R 1 Corresponding alkene, substituted alkene or aromatic hydrocarbon, R 2 Corresponding CH 2 ＝CH(OR 3 ) 3 And performing hydrosilylation reaction. Alternatively, polyfluoroThe siloxane can be prepared from hydrogen-containing silicone oil Me 3 SiO(SiOMeH) a+c (SiOMeR 1 ) b SiMe 3 Respectively with R f Corresponding perfluoropolyether alkenyl, R 2 Corresponding CH 2 ＝CH(OR 3 ) 3 And performing hydrosilylation reaction.
In the present application, the slipping fingerprint-resistant liquid further comprises 99.2-99.99% fluorine-containing diluent and 0.01-0.8% main agent by 100% by weight, and still further comprises 99.4-99.9% fluorine-containing diluent and 0.1-0.6% main agent, wherein the main agent may be any one of 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, 0.22%, 0.25%, 0.27%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6% by weight. If the concentration of the main agent is too low, the anti-fingerprint effect cannot be exerted or the anti-fingerprint performance is poor, and if the concentration of the main agent is too high, the cost is too high and the improvement of the performance is not obvious.
The fluorine-containing diluent can be used for diluting the main agent, and can also protect the main agent from being failed due to premature reaction with moisture. In a preferred embodiment of the present application, the fluorine-containing diluent is not particularly limited, and may be selected from one or a combination of several of perfluorohexane, perfluoroheptane, perfluorooctane, hexafluoropropylene trimer, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, perfluoropentane, perfluorohexane, ethyl perfluorobutyl ether and ethyl nonafluorobutyl ether, and may also be selected from perfluorocyclic ethers such as FC-77.
The perfluoropolyether silane coupling agent is used as one of main components of a main agent, and has good fingerprint resistance, wear resistance and certain smoothness. The perfluoropolyether silane coupling agent in the present application is not particularly limited, and may be any of the prior art, for example, may be any of the existing commercial products such as X-71-197 of Xinyue, dajin UD509, etc., or may be selected from PFPECH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 、PFPECH 2 OCH 2 CH 2 CH[CH 2 CH 2 Si(OCH 3 ) 3 ] 2 、PFPECH 2 OCH[CH 2 CH 2 Si(OCH 3 ) 3 ] 2 Or PFPECH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 Wherein PFPE represents a perfluoropolyether segment, and may be, for example, any one of a D-type perfluoropolyether segment, a Z-type perfluoropolyether segment, a K-type perfluoropolyether segment, and a Y-type perfluoropolyether segment, or a perfluoropolyether segment of other structure, and the average molecular weight of the perfluoropolyether segment may be 500 to 2000. The structure of the D-type perfluoropolyether segment can be CF 3 CF 2 CF 2 O(CF 2 CF 2 CF 2 O) m CF 2 CF 2 The structure of the Z-perfluoropolyether segment can be CF 3 (C 2 F 4 O) x (CF 2 O) y CF 2 The structure of the K-type perfluoropolyether segment can be CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) n CF(CF 3 ) The structure of the Y-type perfluoropolyether segment can be CF 3 O(C 3 F 6 O) p (CF 2 O) q CF 2 -。
In a preferred embodiment of the present application, the weight ratio of perfluoropolyether silane coupling agent to polyfluorosiloxane is 10-100:1, further, the weight ratio may be 10-50:1, for example, the weight ratio may be any one of 10:1, 15:1, 18:1, 20:1, 23:1, 25:1, 27:1, 30:1, 33:1, 35:1, 40:1, 45:1, 50:1, etc.
In a preferred embodiment of the present application, the structure of the perfluoropolyether segment is selected from one of the D-type perfluoropolyether segment, the Z-type perfluoropolyether segment, the K-type perfluoropolyether segment, and the Y-type perfluoropolyether segment, or the perfluoropolyether segment of other structure. The structures of the D-type perfluoropolyether segment, the Z-type perfluoropolyether segment, the K-type perfluoropolyether segment, and the Y-type perfluoropolyether segment are each as described above.
In a preferred embodiment of the present application, the C8-C20 perfluoroalkyl segment has the structure CF 3 (CF 2 ) n CH 2 CH 2 -n=5-17. The linear perfluoroalkyl chain segment has better fingerprint resistance.
In a preferred embodiment of the present application, the values of a, b, c satisfy: a/(a+b+c) is more than or equal to 0.7 and less than or equal to 0.9. When the values of a, b, c satisfy the above ranges, the anti-fingerprint performance of the anti-fingerprint liquid is not substantially affected. Specifically, the value of a/(a+b+c) may be any of 0.7, 0.72, 0.74, 0.75, 0.76, 0.77, 0.78, 0.8, 0.82, 0.83, 0.84, 0.86, 0.88, 0.9, and the like.
In a preferred embodiment of the present application, the values of a, b, c satisfy: b/(a+b+c) is less than or equal to 0.05 and less than or equal to 0.2. When the values of a, b and c meet the above range, the anti-fingerprint liquid slipping performance is obviously improved. Specifically, the value of b/(a+b+c) may be any of 0.05, 0.07, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, and the like.
In a preferred embodiment of the present application, the values of a, b, c satisfy: c/(a+b+c) is less than or equal to 0.03 and less than or equal to 0.1. When the values of a, b, c satisfy the above ranges, the abrasion resistance against the fingerprint liquid has little or no effect. Specifically, the value of c/(a+b+c) may be any of 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, 0.095, 0.1, and the like.
On the other hand, the application provides the preparation method of the smooth anti-fingerprint liquid in any one of the technical schemes, wherein the perfluoropolyether silane coupling agent and the polyfluoropolysiloxane are added into the fluorine-containing diluent and stirred and mixed uniformly;
or,
the perfluoropolyether silane coupling agent and the polyfluoropolysiloxane are added into part of the fluorine-containing diluent, and are uniformly mixed, and then are uniformly mixed with the rest of the fluorine-containing diluent before use.
The following describes the technical scheme of the present application in detail with reference to preparation examples, examples and comparative examples.
Preparation examples 1-4 preparation of polyfluorosiloxanes
Preparation example 1
0.01mol of hydrogen-containing silicone oil Me 3 SiO(SiOMeH) 35.8 (SiOMe 2 ) 4.1 SiMe 3 And 0.33mol of perfluoropolyether allyl ether F (CFCF) 3 CF 2 O) n CFCF 3 CH 2 OCH 2 CH＝CH 2 (average molecular weight 2700) is added into a reaction vessel, the temperature is raised to 90 ℃ under the protection of nitrogen, karstedt catalyst (15 ppm based on the Pt amount) is added, the reaction is maintained at 130-135 ℃ for 5 hours, 0.04mol of vinyl trimethoxy silane is continuously added, the reaction is carried out for 3 hours at constant temperature, the pressure is reduced to below-0.099 MPa, low boiling substances are removed, and the temperature is reduced, so as to obtain the polyfluorisiloxane.
Preparation example 2
0.01mol of hydrogen-containing silicone oil Me 3 SiO(SiOMeH) 40.8 SiMe 3 And 0.33mol of the perfluoropolyether allyl ether in preparation example 1 is added into a reaction vessel, the temperature is raised to 90 ℃ under the protection of nitrogen, a Karstedt catalyst (15 ppm based on the amount of Pt) is added, the reaction is maintained at 130-135 ℃ for 5 hours, 0.04mol of 1-dodecene is continuously added, the constant temperature reaction is carried out for 4 hours, 0.04mol of vinyltrimethoxysilane and the Karstedt catalyst (5 ppm based on the amount of Pt) are continuously added, the constant temperature reaction is carried out for 3 hours, the pressure is reduced to below-0.099 MPa to remove low-boiling-point substances, and the temperature is reduced, so that the polyfluoropolysiloxane is obtained.
Preparation example 3
0.01mol of hydrogen-containing silicone oil Me 3 SiO(SiOMeH) 36.5 (SiOMeR 4 ) 4.3 SiMe 3 (R 4 3-chloropropyl) and 0.33mol of the perfluoropolyether allyl ether of the preparation example 1 are added into a reaction vessel, the temperature is raised to 90 ℃ under the protection of nitrogen, a Karstedt catalyst (15 ppm of the addition amount according to the Pt amount) is added, the reaction is maintained at 130-135 ℃ for 5 hours, 0.04mol of vinyl trimethoxy silane is continuously added, the reaction is carried out for 3 hours at constant temperature, the pressure is reduced to below-0.099 MPa, low-boiling-point substances are removed, and the temperature is reduced, so that the polyfluorisiloxane is obtained.
Preparation example 4
0.01mol of hydrogen-containing silicone oil Me 3 SiO(SiOMeH) 63.2 (SiOMeR 5 ) 6.9 SiMe 3 (R 5 3-chloropropyl) and 0.56mol of the perfluoropolyether allyl ether of preparation example 1 are added into a reaction vessel, the temperature is raised to 90 ℃ under the protection of nitrogen, a Karstedt catalyst (15 ppm of addition amount based on Pt) is added, the temperature is maintained between 130 and 135 ℃ for 6 hours, 0.09mol of vinyltrimethoxysilane is continuously added for reaction for 3 hours at constant temperature, and the pressure is reduced to-0.099 MPaRemoving low-boiling substances, and cooling to obtain the polyfluorosiloxane.
Example 1
Under the protection of nitrogen, 99.8g of methyl nonafluorobutyl ether and 0.2g of main agent are mixed and stirred for 5min to obtain the anti-fingerprint liquid.
The main agent is PFPECH as a perfluoropolyether silane coupling agent 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (average molecular weight 3640) and the polyfluorosiloxane of preparation example 1 were composed in a weight ratio of 20:1.
Example 2
The differences between example 2 and example 1 are: in example 1, the polyfluoro siloxane of preparation example 1 was replaced with an equal weight of polyfluoro siloxane of preparation example 2. The remaining steps remain unchanged.
Example 3
Example 3 differs from example 1 in that: in example 1, the polyfluoro siloxane of preparation example 1 was replaced with an equal weight of polyfluoro siloxane of preparation example 3. The remaining steps remain unchanged.
Example 4
Example 4 differs from example 1 in that: in example 1, the polyfluoro siloxane of preparation example 1 was replaced with an equal weight of polyfluoro siloxane of preparation example 4. The remaining steps remain unchanged.
Example 5
The differences between example 5 and example 3 are: the main agent consists of perfluoropolyether silane coupling agent and polyfluorosiloxane according to the weight ratio of 20:1, and the composition is adjusted to be 10:1. The remaining steps remain unchanged.
Example 6
The differences between example 6 and example 3 are: the main agent consists of perfluoropolyether silane coupling agent and polyfluorosiloxane according to the weight ratio of 20:1, and the composition is adjusted to 50:1. The remaining steps remain unchanged.
Example 7
The differences between example 7 and example 3 are: the main agent consists of perfluoropolyether silane coupling agent and polyfluorosiloxane according to the weight ratio of 20:1, and the composition is adjusted to 90:1. The remaining steps remain unchanged.
Comparative example 1
The difference between comparative example 1 and example 1 is: in example 1, the main agent was replaced with an equal weight of the polyfluorosiloxane of preparation example 3. The remaining steps remain unchanged.
Comparative example 2
The difference between comparative example 2 and example 1 is: in example 1, the main agent was replaced with an equal weight of the polyfluorosiloxane of preparation example 4. The remaining steps remain unchanged.
Comparative example 3
The difference between comparative example 3 and example 1 is: in example 1, the polyfluoropolysiloxane of preparation example 1 was replaced with an equivalent weight of the perfluoropolyether silane coupling agent of example 1. The remaining steps remain unchanged.
Example 8
Under the protection of nitrogen, 99.85g of perfluorohexane and 0.15g of main agent are mixed and stirred for 5min to obtain the anti-fingerprint liquid.
The main agent consists of the perfluoropolyether silane coupling agent of the example 1 and the polyfluorosiloxane of the preparation example 3 according to the weight ratio of 25:1.
Example 9
Under the protection of nitrogen, 99.75g of perfluorohexane and 0.25g of main agent are mixed and stirred for 5min to obtain the anti-fingerprint liquid.
The main agent consists of the perfluoropolyether silane coupling agent of the example 1 and the polyfluorosiloxane of the preparation example 3 according to the weight ratio of 25:1.
Comparative example 4
The difference between comparative example 4 and example 9 is: in example 9, the main agent was replaced with an equal weight of the polyfluorosiloxane of preparation example 3. The remaining steps remain unchanged.
Comparative example 5
The difference between comparative example 5 and example 9 is: in example 9, the main agent was replaced with an equal weight of the perfluoropolyether silane coupling agent of example 1. The remaining steps remain unchanged.
Performance testing
The anti-fingerprint solutions of examples 1-9 and comparative examples 1-5 were sprayed directly onto clean glass cover plates, placed in a 130 ℃ ring oven for 20 minutes, removed, and placed at room temperature for 24 hours.
Oil repellency: n-hexadecane was dropped on the treated glass cover plate, and the contact angle was measured with a water drop angle tester. Testing is carried out at 5 positions in the middle and around the glass cover plate respectively, and the testing results are averaged. The higher the contact angle of n-hexadecane, the better the oil repellency.
Fingerprint protection rating: lightly pressing the treated glass cover plate with an index finger for 5s, and observing fingerprint residues after removing the finger for 3 s: grade 5-no trace; grade 4-slight mark, which can be easily erased with a finger; grade 3-slight mark, not erasable with the finger; grade 2-obvious trace; grade 1-obvious trace.
Slip degree: and testing the dynamic friction coefficient of the surface of the treated glass cover plate by adopting a dynamic friction coefficient tester. The lower the coefficient of dynamic friction, the better the smoothness.
Abrasion resistance: and testing by adopting an abrasion resistance tester. 1Kg load, 0000# steel wool, contact area 10mm x 10mm, frequency 60 times/min. After 3000 times of friction, the water drop angle reaches 100 degrees and above, and the test is passed, otherwise, the test is not passed.
The results are shown in Table 1.
TABLE 1
| N-hexadecane contact angle/° | Fingerprint resistant rating | Coefficient of dynamic friction | Wear resistance | |
| Example 1 | 76 | 5 | 0.029 | By passing through |
| Example 2 | 71 | 5 | 0.027 | By passing through |
| Example 3 | 74 | 5 | 0.024 | By passing through |
| Example 4 | 76 | 5 | 0.023 | By passing through |
| Example 5 | 72 | 4 | 0.022 | By passing through |
| Example 6 | 76 | 5 | 0.027 | By passing through |
| Example 7 | 77 | 5 | 0.031 | By passing through |
| Comparative example 1 | 63 | 3 | 0.021 | Failed to pass |
| Comparative example 2 | 65 | 3 | 0.020 | Failed to pass |
| Comparative example 3 | 78 | 5 | 0.033 | By passing through |
| Example 8 | 72 | 4 | 0.025 | By passing through |
| Example 9 | 76 | 5 | 0.026 | By passing through |
| Comparative example 4 | 67 | 4 | 0.022 | Failed to pass |
| Comparative example 5 | 79 | 5 | 0.035 | By passing through |
As is clear from the results in Table 1, the anti-fingerprint liquid of the present application has a lower dynamic friction coefficient, has better slipping property, and has little influence on the anti-fingerprint property although the contact angle of n-hexadecane is reduced to some extent.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. The smooth fingerprint resisting liquid is characterized by comprising 99-99.999% of fluorine-containing diluent and 0.001-1% of main agent by weight of 100%;
the main agent consists of a perfluoropolyether silane coupling agent and polyfluorosiloxane shown in the following formula (1) according to the weight ratio of 5-100:1,
Me 3 SiO(SiOMeR f ) a (SiOMeR 1 ) b (SiOMeR 2 ) c SiMe 3 (1)
wherein R is f Represents a perfluoropolyether segment or a C8-C20 perfluoroalkyl segment, R 1 Selected from C1-C12 alkyl, chloro-substituted C3-C6 alkyl or C6-C12 aryl, R 2 Is of the structure-CH 2 CH 2 Si(OR 3 ) 3 ，R 3 Selected from methyl or ethyl, me represents methyl, a=10-100, b=3-10, c=3-8.
2. The smooth anti-fingerprint liquid of claim 1, wherein the fluorine-containing diluent is selected from one or more of perfluorohexane, perfluoroheptane, perfluorooctane, hexafluoropropylene trimer, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, perfluoropentane, perfluorohexane, ethyl perfluorobutyl ether, and ethyl nonafluorobutyl ether.
3. The slip fingerprint resistant fluid of claim 1 wherein the perfluoropolyether silane coupling agent is selected from the group consisting of PFPECH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 、PFPECH 2 OCH 2 CH 2 CH[CH 2 CH 2 Si(OCH 3 ) 3 ] 2 、PFPECH 2 OCH[CH 2 CH 2 Si(OCH 3 ) 3 ] 2 Or PFPECH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 Wherein PFPE represents a perfluoropolyether segment.
4. The smooth anti-fingerprint liquid of claim 1, wherein the weight ratio of the perfluoropolyether silane coupling agent to the polyfluoropolysiloxane is 10-100:1.
5. The smooth anti-fingerprint liquid of claim 1, wherein the structure of the perfluoropolyether segment is selected from one of a D-type perfluoropolyether segment, a Z-type perfluoropolyether segment, a K-type perfluoropolyether segment, and a Y-type perfluoropolyether segment.
6. The smooth anti-fingerprint liquid of claim 1, wherein the C8-C20 perfluoroalkyl segment has the structure CF 3 (CF 2 ) n CH 2 CH 2 -，n=5-17。
7. The smooth anti-fingerprint liquid of claim 1, wherein the values of a, b, c satisfy: a/(a+b+c) is more than or equal to 0.7 and less than or equal to 0.9.
8. The smooth anti-fingerprint liquid of claim 1, wherein the values of a, b, c satisfy: b/(a+b+c) is less than or equal to 0.05 and less than or equal to 0.2.
9. The smooth anti-fingerprint liquid of claim 1, wherein the values of a, b, c satisfy: c/(a+b+c) is less than or equal to 0.03 and less than or equal to 0.1.
10. The method for preparing a smooth anti-fingerprint liquid according to any one of claims 1 to 9, characterized in that the perfluoropolyether silane coupling agent and the polyfluoropolysiloxane are added into the fluorine-containing diluent and stirred and mixed uniformly;
or,
and adding the perfluoropolyether silane coupling agent and the polyfluoropolysiloxane into part of the fluorine-containing diluent, uniformly mixing, and uniformly mixing with the rest of the fluorine-containing diluent before use.
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