CN117417524A - Perfluoro polyether polyalkoxysilane compound and fingerprint-resistant surface treatment liquid - Google Patents
Perfluoro polyether polyalkoxysilane compound and fingerprint-resistant surface treatment liquid Download PDFInfo
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- CN117417524A CN117417524A CN202311557082.5A CN202311557082A CN117417524A CN 117417524 A CN117417524 A CN 117417524A CN 202311557082 A CN202311557082 A CN 202311557082A CN 117417524 A CN117417524 A CN 117417524A
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- perfluoropolyether
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- polyalkoxysilane compound
- surface treatment
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- 239000010702 perfluoropolyether Substances 0.000 title claims abstract description 120
- 150000001875 compounds Chemical class 0.000 title claims abstract description 52
- 238000004381 surface treatment Methods 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 title claims abstract description 18
- 230000003666 anti-fingerprint Effects 0.000 claims abstract description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 42
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 239000003085 diluting agent Substances 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
- -1 R 3 Selected from H Chemical group 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 9
- 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 7
- 239000007822 coupling agent Substances 0.000 claims description 7
- 125000000204 (C2-C4) acyl group Chemical group 0.000 claims description 6
- 229960004624 perflexane Drugs 0.000 claims description 6
- 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 6
- 238000006957 Michael reaction Methods 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- 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 3
- 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
- 238000000034 method Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 3
- 239000011521 glass Substances 0.000 abstract description 10
- 239000006116 anti-fingerprint coating Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEXHLHNCJVXPNU-UHFFFAOYSA-N 2-(trimethoxysilylmethyl)butane-1,4-diamine Chemical compound CO[Si](OC)(OC)CC(CN)CCN HEXHLHNCJVXPNU-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000199 molecular distillation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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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
- C09D171/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (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 specifically provides a perfluoropolyether polyalkoxysilane compound and an anti-fingerprint surface treatment liquid. The structure of the perfluoropolyether polyalkoxysilane compound is
Description
Technical Field
The application relates to the technical field of anti-fingerprint materials, in particular to a perfluoropolyether polyalkoxysilane compound and an anti-fingerprint surface treatment liquid.
Background
The silane coupling agent containing the perfluoropolyether has the characteristics of unique chemical stability, low friction coefficient, low surface tension, good light transmittance, good weather resistance and the like, and is widely applied to the surface treatment of a touch screen so as to provide fingerprint resistance and other effects, and prevent the touch screen from being polluted by fingerprints, sweat, cosmetics and the like, and the attractive appearance and the use are influenced.
The silane coupling agent containing the perfluoropolyether is hydrolyzed by virtue of alkoxy in the silane coupling agent and is subjected to condensation reaction with hydroxyl on the surface of the touch screen, so that the nanoscale anti-fingerprint coating is obtained. As a screen which is frequently touched, the wear resistance of the anti-fingerprint coating is an important performance index, and has a remarkable relation with the hydrolytic condensation capability of alkoxy groups in the silane coupling agent containing perfluoropolyether. The prior art reports a number of methods for improving the abrasion resistance of anti-fingerprint coatings, the perfluoropolyether siloxane compounds disclosed in document one have the following structure,
wherein the PFPE is a perfluoropolyether chain; and R is chlorine, methoxy or ethoxy. However, since the silicon content is high, the fingerprint resistance is deteriorated although the abrasion resistance is good. Document II discloses perfluoropolyether-modified silane compounds having the following structure: r is R f CH 2 O(CH 2 ) p C{(CH 2 ) q OC(O)NH(CH 2 ) 3 Si(OCH 3 ) 3 } 3 、R f CH 2 OCH 2 C{CH 2 OC(O)NH(CH 2 ) 3 Si(OCH 3 ) 3 } 3 Or R is f (CH 2 ) 3 OCH 2 C{CH 2 OC(O)NH(CH 2 ) 3 Si(OCH 3 ) 3 } 3 Wherein R is f Represents F (CF) 2 CF 2 O) m (CF 2 O) n CF 2 The binding force of the base material is also improved by a plurality of alkoxy silicon groups at the molecular terminal, so that the wear resistance can be improved.
Document one: chinese patent application CN116854902a.
And II, literature: chinese invention patent CN105778080B.
Disclosure of Invention
The wear resistance of the anti-fingerprint coating determines the service life of the anti-fingerprint coating, and therefore, the application provides the perfluoropolyether silane and the anti-fingerprint surface treatment liquid, which have better wear resistance.
The application adopts the following technical scheme:
a perfluoropolyether polyalkoxysilane compound having a structure represented by the following formula (1),
wherein PFPE is a perfluoropolyether segment, R 1 And R is 2 Independently selected from C1-C4 alkyl or C2-C4 acyl, R 3 Selected from H, C1-C4 alkyl or
R 4 Selected from C1-C4 alkyl or C2-C4 acyl, x=0-1, y=3-6.
Preferably, the perfluoropolyether polyalkoxysilane compound is obtained by carrying out michael reaction on perfluoropolyether allyl ether and a primary amino silane coupling agent, and then carrying out ring opening reaction on the perfluoropolyether allyl ether and a gamma-glycidoxypropyl silane coupling agent.
More preferably, the molar ratio of the perfluoropolyether allyl ether to the primary amino silane-containing coupling agent is 1:1-3.
More preferably, the primary amino silane-containing coupling agent has the general formula NH 2 (CH 2 CH 2 NH) x (CH 2 ) y Si(OR 1 ) 3 。
More preferably, the molar ratio of the perfluoropolyether allyl ether to the gamma-glycidoxypropyl silane coupling agent is 1:1-5.
An anti-fingerprint surface treatment liquid consists of 99-99.999% fluorine diluent and 0.001-1% main agent according to 100% by weight; the perfluoropolyether polyalkoxysilane compound according to any one of the above technical solutions accounts for 10 to 100% by weight of the main agent.
Preferably, the weight ratio of the perfluoropolyether polyalkoxysilane compound in the main agent is 30-80%.
Preferably, the main agent further comprises 20 to 70% by weight of a perfluoropolyether silane coupling agent.
More preferably, 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.
Preferably, the fluorine diluent is selected from one or a combination of more of perfluorohexane, perfluoroheptane, perfluoropentane, perfluorooctane, hexafluoropropylene trimer, methyl nonafluorobutyl ether, ethyl perfluorobutyl ether, perfluoro cyclic ether and ethyl nonafluorobutyl ether.
In summary, the present application has the following beneficial effects:
1. the molecule of the perfluoropolyether polyalkoxysilane compound contains two or more trialkoxy silicon groups, and the coating can realize higher binding force after being coated on the surface of a substrate such as glass and the like and dried.
2. The molecule of the perfluoropolyether polyalkoxysilane compound contains secondary amino groups and/or tertiary amino groups, so that the hydrolytic condensation of alkoxy silicon groups can be promoted, and the binding force of the perfluoropolyether polyalkoxysilane compound on substrates such as glass and the like can be improved.
3. In the application, different trialkoxy silicon groups in the same molecule of the perfluoropolyether polyalkoxy silane compound are far away, so that hydrolytic condensation of the trialkoxy silicon groups among the molecules of the different perfluoropolyether polyalkoxy silane compounds is facilitated, and better performance of the perfluoropolyether polyalkoxy silane compounds is realized.
4. The anti-fingerprint surface treatment liquid is coated on the surface of a base material such as glass, and has excellent wear resistance, good anti-fingerprint property and smoothness.
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 present application provides a perfluoropolyether polyalkoxysilane compound having a structure represented by the following formula (1),
wherein PFPE is a perfluoropolyether segment, R 1 And R is 2 Independently selected from C1-C4 alkyl or C2-C4 acyl, R 3 Selected from H, C1-C4 alkyl or
R 4 Selected from C1-C4 alkyl or C2-C4 acyl, x=0-1, y=3-6.
The molecule structure of the perfluoropolyether polyalkoxysilane compound has the following characteristics: (1) Containing two or more trialkoxysilyl groups can realize excellent binding force with base materials such as glass; (2) The tertiary amino and/or secondary amino is used as an alkaline component, so that the hydrolysis and condensation of trialkoxy silicon groups can be promoted, the formation of excellent binding force with base materials such as glass and the like can be accelerated, and the promotion of the binding force can be promoted; (3) The distance between two or more trialkoxy silicon groups is far, so that the hydrolytic condensation of the trialkoxy silicon groups in the same molecule of the perfluoropolyether polyalkoxy silane compound can be weakened or avoided, and the interaction force between different molecules of the perfluoropolyether polyalkoxy silane compound can be improved.
As used herein, perfluoropolyether segments refer to the backbone chain generally consisting of-CF 2 O-、-CF 2 CF 2 O-、-CF 2 CF 2 CF 2 O-and/or-CFCF 3 CF 2 The O-such ether chain may be constituted by, 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 another structure,the average molecular weight of the perfluoropolyether segment can be 800 to 4000. 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 perfluoropolyether polyalkoxysilane compound is obtained by a michael reaction of a perfluoropolyether allyl ether with a primary aminosilane-containing coupling agent followed by a ring opening reaction with a gamma-glycidoxypropyl silane coupling agent. The perfluoro polyether allyl ether firstly carries out michael reaction with a primary amino silane coupling agent, the primary amino group is converted into a secondary amino group, then the gamma-glycidyl ether oxypropyl silane coupling agent is grafted onto the perfluoro polyether polyalkoxy silane compound by utilizing the high reactivity of the secondary amino group and the epoxy group, and more trialkoxy silicon groups are introduced.
In a more preferred embodiment of the present application, the molar ratio of perfluoropolyether allyl ether to primary amino-containing silane coupling agent is 1:1-3. The excessive primary amino silane coupling agent is compared with the perfluoropolyether allyl ether, so that the complete reaction of the perfluoropolyether allyl ether can be promoted, and the excessive primary amino silane coupling agent can be removed by various modes such as reduced pressure distillation, molecular distillation and the like. Further, the molar ratio of perfluoropolyether allyl ether to primary amino-containing silane coupling agent is 1:1.2-3, for example, the molar ratio may be any of 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3, etc.
In a more preferred embodiment of the present application, the primary amino silane-containing coupling agent has the formula NH 2 (CH 2 CH 2 NH) x (CH 2 ) y Si(OR 1 ) 3 . For example, the primary amino-containing silane coupling agent may be 3-aminopropyl trimethoxysilane, beta-aminoethyl-gamma-aminopropyl trimethoxysilane, or the like. After the primary amino-containing silane coupling agent and the perfluoropolyether allyl ether are subjected to Michael addition reaction, the product contains 1 or more secondary amino groups, and can be subjected to ring opening reaction with 1 or more gamma-glycidyl ether oxypropyl silane coupling agents.
In a more preferred embodiment of the present application, the molar ratio of perfluoropolyether allyl ether to gamma-glycidoxypropyl silane coupling agent is from 1:1 to 5. The gamma-glycidoxypropyl silane coupling agent can be excessive relative to the perfluoropolyether allyl ether, and the excessive gamma-glycidoxypropyl silane coupling agent can be removed by means of reduced pressure distillation, molecular distillation and the like. For example, when the perfluoropolyether allyl ether contains 1 secondary amino group, the molar ratio of the perfluoropolyether allyl ether to the gamma-glycidoxypropyl silane coupling agent may be 1:1-3, where 1 perfluoropolyether allyl ether molecule can react only with 1 gamma-glycidoxypropyl silane coupling agent molecule, for example, the molar ratio may be any of 1:1, 1:1.3, 1:1.5, 1:1.7, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3, etc.; when the perfluoropolyether allyl ether contains 2 or more secondary amino groups, the molar ratio of the perfluoropolyether allyl ether to the gamma-glycidoxypropyl silane coupling agent may be 1:1-5, in which case 1 perfluoropolyether allyl ether molecule may be reacted with 1 or more gamma-glycidoxypropyl silane coupling agent molecules, for example, the molar ratio may be any of 1:1, 1:1.3, 1:1.5, 1:1.7, 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3, 1:3.3, 1:3.5, 1:3.7, 1:4, 1:4.2, 1:4.4, 1:4.5, 1:4.7, 1:5, etc.
On the other hand, the application provides an anti-fingerprint surface treatment liquid which consists of 99-99.999% of fluorine diluent and 0.001-1% of main agent by weight percent;
the perfluoropolyether polyalkoxysilane compound according to any one of the above technical solutions, wherein the weight ratio of the main agent is 10-100%.
Further, the fingerprint-resistant surface treatment liquid consists of 99 to 99.99% fluorine diluent and 0.01 to 1% of main agent, or further consists of 99.4 to 99.9% fluorine diluent and 0.1 to 0.6% of main agent, for example, 99.9% fluorine diluent and 0.1% of main agent, 99.85% fluorine diluent and 0.15% of main agent, 99.8% fluorine diluent and 0.2% of main agent, 99.7% fluorine diluent and 0.3% of main agent, 99.6% fluorine diluent and 0.4% of main agent, 99.5% fluorine diluent and 0.5% of main agent, 99.4% fluorine diluent and 0.6% of main agent, and the like, by 100% by weight. From the comprehensive dimension of cost and performance, the concentration of the main agent in the anti-fingerprint surface treatment liquid is generally 0.2-0.3% by weight, the concentration is too low, the anti-fingerprint, wear resistance, slipping performance and the like are poor, the concentration is improved, the improvement on the performance is limited, but the cost is obviously increased.
In a preferred embodiment of the present application, the perfluoropolyether polyalkoxysilane compound is present in an amount of 30 to 80% by weight of the base agent. For example, the weight ratio of the perfluoropolyether polyalkoxysilane compound to the main agent may be any of 30%, 40%, 45%, 50%, 60%, 65%, 70%, 75%, 80%, etc.
In a preferred embodiment of the present application, the base agent further comprises 20 to 70% by weight of a perfluoropolyether silane coupling agent.
In a more preferred embodiment of the present application, 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, wherein the perfluoropolyether segment is as described above. Alternatively, the perfluoropolyether silane coupling agent of the present application may be directly an existing commercially available product such as X-71-197 of Xinyue, dajin UD509, or the like.
In a preferred embodiment of the present application, the fluorine diluent is not particularly limited, and may be selected from one or a combination of several of perfluorohexane, perfluoroheptane, perfluoropentane, perfluorooctane, hexafluoropropylene trimer, methyl nonafluorobutyl ether, ethyl perfluorobutyl ether, perfluoro cyclic ether and ethyl nonafluorobutyl ether.
The technical scheme of the application is described in detail below with reference to examples and comparative examples.
EXAMPLES 1-5 preparation of perfluoropolyether polyalkoxysilane compounds
Example 1
0.01mol of perfluoropolyether allyl ether CF 3 CF 2 O(CF 2 CF 2 O) m (CF 2 O) n CF 2 CH 2 OCH 2 CH＝CH 2 (average molecular weight 3100) and 0.02mol of 3-aminopropyl trimethoxy silane are added into a reaction vessel, the temperature is raised to 100 ℃ under the stirring of 300rpm, the reaction is carried out for 120 hours at constant temperature, the pressure is reduced to below-0.099 MPa, unreacted 3-aminopropyl trimethoxy silane is removed, and the temperature is reduced, so that an intermediate product is obtained.
0.01mol of the intermediate product and 0.02mol of silane coupling agent KH-560 are added into a reaction vessel, stirred for 1 hour at room temperature, heated to 70 ℃ and stirred for 2 hours, depressurized to below-0.099 MPa, heated to 150 ℃ and removed of low-boiling substances, thus obtaining the perfluoropolyether polyalkoxysilane compound.
Example 2
Adding 0.01mol of perfluoropolyether allyl ether and 0.03mol of beta-aminoethyl-gamma-aminopropyl trimethoxysilane in the embodiment 1 into a reaction vessel, heating to 100 ℃ under stirring at 300rpm, reacting at constant temperature for 120h, decompressing to below-0.099 MPa, heating to 150 ℃ to remove unreacted beta-aminoethyl-gamma-aminopropyl trimethoxysilane, and cooling to obtain an intermediate product.
0.01mol of the above intermediate and 0.01mol of a silane coupling agent KH-560 were added to a reaction vessel, stirred at room temperature for 1 hour, heated to 70℃and stirred for 2 hours to obtain a perfluoropolyether polyalkoxysilane compound.
Example 3
The differences between example 3 and example 2 are: in example 2, KH-560 was adjusted from 0.01mol to 0.015mol. The remaining steps remain unchanged.
Example 4
The differences between example 4 and example 2 are: in example 2, KH-560 was adjusted from 0.01mol to 0.02mol. The remaining steps remain unchanged.
Example 5
0.01mol of the intermediate product in example 2 and 0.04mol of a silane coupling agent KH-560 are added into a reaction vessel, stirred at room temperature for 1 hour, heated to 70 ℃ and stirred for 2 hours, depressurized to below-0.099 MPa, heated to 150 ℃ and removed of low boiling substances, thereby obtaining the perfluoropolyether polyalkoxysilane compound.
Examples 6 to 15 preparation of anti-fingerprint surface treatment liquid
Example 6
99.8g of perfluorohexane as a fluorine diluent and 0.2g of the perfluoropolyether polyalkoxysilane compound obtained in example 1 were added to a reaction vessel under a nitrogen atmosphere, and stirred and mixed uniformly to obtain an anti-fingerprint surface treatment liquid.
Example 7
The differences between example 7 and example 6 are: in example 6, the perfluoropolyether polyalkoxysilane compound obtained in example 1 was replaced with the perfluoropolyether polyalkoxysilane compound obtained in example 2. The remaining steps remain unchanged.
Example 8
The differences between example 8 and example 6 are: in example 6, the perfluoropolyether polyalkoxysilane compound obtained in example 1 was replaced with the perfluoropolyether polyalkoxysilane compound obtained in example 3. The remaining steps remain unchanged.
Example 9
The differences between example 9 and example 6 are: in example 6, the perfluoropolyether polyalkoxysilane compound obtained in example 1 was replaced with the perfluoropolyether polyalkoxysilane compound obtained in example 4. The remaining steps remain unchanged.
Example 10
The differences between example 10 and example 6 are: in example 6, the perfluoropolyether polyalkoxysilane compound obtained in example 1 was replaced with the perfluoropolyether polyalkoxysilane compound obtained in example 5. The remaining steps remain unchanged.
Example 11
The differences between example 11 and example 6 are: in example 6, 0.2g of the perfluoropolyether polyalkoxysilane compound obtained in example 1 was replaced with 0.08g of the perfluoropolyether polyalkoxysilane compound obtained in example 4 and 0.12g of the perfluoropolyether silane coupling agent PFPECH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (PFPE is a Z-type perfluoropolyether segment with an average molecular weight of 3100). The remaining steps remain unchanged.
Example 12
The differences between example 12 and example 6 are: in example 6, 0.2g of the perfluoropolyether polyalkoxysilane compound obtained in example 1 was replaced with a combination of 0.12g of the perfluoropolyether polyalkoxysilane compound obtained in example 4 and 0.08g of the perfluoropolyether silane coupling agent in example 11. The remaining steps remain unchanged.
Example 13
The differences between example 13 and example 6 are: in example 6, 0.2g of the perfluoropolyether polyalkoxysilane compound obtained in example 1 was replaced with a combination of 0.16g of the perfluoropolyether polyalkoxysilane compound obtained in example 4 and 0.04g of the perfluoropolyether silane coupling agent of example 11. The remaining steps remain unchanged.
Comparative example 1
The difference between comparative example 1 and example 6 is: in example 6, 0.2g of the perfluoropolyether polyalkoxysilane compound obtained in example 1 was replaced with 0.2g of the perfluoropolyether silane coupling agent of example 11. The remaining steps remain unchanged.
Comparative example 2
Under the nitrogen atmosphere, 0.2g of the intermediate product of the embodiment 1 and 99.8g of perfluorohexane are added into a reaction vessel, and the mixture is stirred and mixed uniformly to obtain the anti-fingerprint surface treatment liquid.
Comparative example 3
Japanese Dajin UD509 anti-fingerprint oil was diluted with perfluorohexane to a main agent concentration of 0.2wt%.
Example 14
99.75g of ethyl perfluorobutyl ether as a fluorine diluent and 0.25g of the perfluoropolyether polyalkoxysilane compound obtained in example 4 were added to a reaction vessel under a nitrogen atmosphere, and stirred and mixed uniformly to obtain an anti-fingerprint surface treatment liquid.
Example 15
The differences between example 15 and example 14 are: in example 14, 0.25g of the perfluoropolyether polyalkoxysilane compound obtained in example 4 was replaced with a combination of 0.15g of the perfluoropolyether polyalkoxysilane compound obtained in example 4 and 0.1g of the perfluoropolyether silane coupling agent of example 11. The remaining steps remain unchanged.
Comparative example 4
The difference between comparative example 4 and example 14 is: in example 14, 0.25g of the perfluoropolyether polyalkoxysilane compound obtained in example 4 was replaced with 0.25g of the perfluoropolyether silane coupling agent of example 11. The remaining steps remain unchanged.
Performance testing
The anti-fingerprint solutions of examples 6-15 and comparative examples 1-4 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.
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 marks, which cannot be wiped clean with fingers; 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. The number of rubs at which the drop angle reaches 100 ° was tested. The drop angle was tested using the drop angle test.
The results are shown in Table 1.
TABLE 1 Performance test results
As is clear from the data in Table 1, the anti-fingerprint coating obtained by applying the anti-fingerprint surface treatment liquid containing the perfluoropolyether polyalkoxysilane compound of the present application to a glass substrate has excellent abrasion resistance and also has excellent anti-fingerprint and slip properties.
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. A perfluoropolyether polyalkoxysilane compound having a structure represented by the following formula (1),
wherein PFPE is a perfluoropolyether segment, R 1 And R is 2 Independently selected from C1-C4 alkyl or C2-C4 acyl, R 3 Selected from H, C1-C4 alkyl or
R 4 Selected from C1-C4 alkyl or C2-C4 acyl, x=0-1, y=3-6.
2. The perfluoropolyether polyalkoxysilane compound according to claim 1, wherein the perfluoropolyether polyalkoxysilane compound is obtained by a michael reaction of perfluoropolyether allyl ether with a primary amino silane-containing coupling agent followed by a ring opening reaction with a gamma-glycidoxypropyl silane coupling agent.
3. The perfluoropolyether polyalkoxysilane compound according to claim 2, wherein the molar ratio of the perfluoropolyether allyl ether to the primary amino silane-containing coupling agent is 1:1-3.
4. The perfluoropolyether polyalkoxysilane compound according to claim 2, wherein the primary amino silane-containing coupling agent has a general formula of NH 2 (CH 2 CH 2 NH) x (CH 2 ) y Si(OR 1 ) 3 。
5. The perfluoropolyether polyalkoxysilane compound according to claim 2, wherein the molar ratio of the perfluoropolyether allyl ether to the gamma-glycidoxypropyl silane coupling agent is 1:1-5.
6. An anti-fingerprint surface treatment liquid is characterized by comprising, by weight, 99-99.999% of fluorine diluent and 0.001-1% of main agent according to 100%;
the perfluoropolyether polyalkoxysilane compound according to any one of claims 1-5, having a weight ratio of 10-100% in the main agent.
7. The anti-fingerprint surface treatment liquid according to claim 6, wherein the weight ratio of the perfluoropolyether polyalkoxysilane compound to the main agent is 30-80%.
8. The anti-fingerprint surface treatment fluid of claim 6, wherein the main agent further comprises 20-70% by weight of a perfluoropolyether silane coupling agent.
9. The anti-fingerprint surface treatment fluid of claim 8, wherein 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, the method comprises the steps of, wherein,
PFPE represents a perfluoropolyether segment.
10. The anti-fingerprint surface treatment fluid according to claim 6, wherein the fluorine diluent is selected from one or a combination of several of perfluorohexane, perfluoroheptane, perfluoropentane, perfluorooctane, hexafluoropropylene trimer, methyl nonafluorobutyl ether, ethyl perfluorobutyl ether, perfluoro cyclic ether and ethyl nonafluorobutyl ether.
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