CN114059045A - Hydrophobic and oleophobic coating, preparation method and product thereof - Google Patents
Hydrophobic and oleophobic coating, preparation method and product thereof Download PDFInfo
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- CN114059045A CN114059045A CN202010766901.7A CN202010766901A CN114059045A CN 114059045 A CN114059045 A CN 114059045A CN 202010766901 A CN202010766901 A CN 202010766901A CN 114059045 A CN114059045 A CN 114059045A
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 86
- 238000000576 coating method Methods 0.000 title claims abstract description 81
- 239000011248 coating agent Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 77
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000007740 vapor deposition Methods 0.000 claims description 7
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 238000009834 vaporization Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 2
- 238000002203 pretreatment Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 17
- 239000001307 helium Substances 0.000 description 8
- 229910052734 helium Inorganic materials 0.000 description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 8
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000003075 superhydrophobic effect Effects 0.000 description 4
- 101001136034 Homo sapiens Phosphoribosylformylglycinamidine synthase Proteins 0.000 description 3
- 102100036473 Phosphoribosylformylglycinamidine synthase Human genes 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- HFNSTEOEZJBXIF-UHFFFAOYSA-N 2,2,4,5-tetrafluoro-1,3-dioxole Chemical compound FC1=C(F)OC(F)(F)O1 HFNSTEOEZJBXIF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical class [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000003666 anti-fingerprint Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001000 nickel titanium Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- DVMSVWIURPPRBC-UHFFFAOYSA-N 2,3,3-trifluoroprop-2-enoic acid Chemical class OC(=O)C(F)=C(F)F DVMSVWIURPPRBC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- -1 perfluorosiloxanes Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a hydrophobic and oleophobic coating, a preparation method thereof and a product, wherein the hydrophobic and oleophobic coating is formed by depositing perfluoropolyether or perfluoropolyether derivatives on the surface of a substrate in a PECVD (plasma enhanced chemical vapor deposition) mode so as to improve the hydrophobic and oleophobic performance of the surface of the substrate through the perfluoropolyether or the perfluoropolyether derivatives.
Description
Technical Field
The invention relates to the field of surface modification, in particular to a hydrophobic and oleophobic coating formed by utilizing a plasma chemical vapor deposition technology, a preparation method thereof and a product.
Background
Nowadays, hydrophobic and oleophobic products are continuously favored by consumers, and more researches on hydrophobic and oleophobic properties are also followed. Among the most studied compounds are perfluorinated compounds (PFASs), which have been widely used in industrial production due to their excellent thermal stability, hydrophobicity and oleophobicity.
However, PFASs have the characteristics of difficult degradation, easy biological accumulation, high toxicity and the like, and become a novel pollutant. The majority of PFASs degradation products are perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), which cause damage to the reproductive, developmental, liver and immune systems of animals and may induce tumor production with adverse effects on human health. Because these perfluorinated compounds are difficult to degrade, many developed countries have promulgated strict restrictions on the use of perfluorinated compounds containing long carbon chains, which has undoubtedly limited the development and application of such hydrophobic and oleophobic coating technologies. How to realize the hydrophobic and oleophobic performance on the fabric and avoid the environmental problem caused by using perfluorinated compounds is a research hotspot in the field of hydrophobic and oleophobic coatings in recent years.
The Chinese patent document with the application publication number of CN107558184A discloses a preparation method of a fabric hydrophobic and oleophobic agent, and raw materials used in the method are non-toxic and harmless and do not irritate human bodies. However, the fabric needs to be soaked in a reaction kettle and a stirring kettle in the synthesis process, so that the impregnation is not uniform easily, and the method is not suitable for application of a formed large fabric finished product.
Chinese patent document with the patent application number of 2019105740043 discloses a fluorine-containing nano polymer modified nickel-titanium alloy material with super-hydrophobic and oleophobic properties and a preparation method thereof, and the surface of the modified nickel-titanium alloy material has excellent super-hydrophobic and super-oleophobic properties; the chinese patent application No. 2018100098455 discloses a method for preparing super-hydrophobic and super-oleophobic thin film material by using an initiation chemical vapor deposition method, and these super-hydrophobic and super-oleophobic materials utilize perfluorocompounds such as perfluoroacrylates and perfluorosiloxanes. This clearly limits the development and application of such hydrophobic and oleophobic coating techniques.
Disclosure of Invention
One advantage of the present invention is to provide a hydrophobic and oleophobic coating, and a method and product for making the same, which improves the hydrophobic and oleophobic properties of a substrate by forming the hydrophobic and oleophobic coating on the surface of the substrate by a plasma enhanced chemical vapor deposition process.
Another advantage of the present invention is to provide a hydrophobic and oleophobic coating, and a method and product for making the same, wherein the hydrophobic and oleophobic coating uses perfluoropolyether or perfluoropolyether derivatives as raw materials.
Another advantage of the present invention is to provide a hydrophobic and oleophobic coating, and methods and products for making the same, wherein the perfluoropolyether can include K, Y, Z, and D structures.
Another advantage of the present invention is to provide a hydrophobic and oleophobic coating, and methods and products for making the same, wherein the perfluoropolyether derivative can be a perfluoropolyether hydroxyl derivative (PFPE-OH) having at least one hydroxyl group.
Another advantage of the present invention is to provide a hydrophobic and oleophobic coating, and method and product for making the same, wherein the perfluoropolyether derivative can be an amorphous perfluorinated homopolymer or copolymer of perfluorodioxole.
Another advantage of the present invention is to provide a hydrophobic and oleophobic coating, and a method and product for making the same, wherein the raw material perfluoropolyether or perfluoropolyether derivative is environmentally friendly, thereby reducing environmental pollution.
To achieve at least one of the above advantages, one aspect of the present invention provides a hydrophobic and oleophobic coating, comprising: and depositing perfluoropolyether or perfluoropolyether derivatives on the surface of a substrate in a PECVD (plasma enhanced chemical vapor deposition) mode to form the hydrophobic and oleophobic coating.
The hydrophobic and oleophobic coating according to an embodiment, wherein the perfluoropolyether structure comprises K type, Y type Z type and D type structures.
A hydrophobic and oleophobic coating according to one embodiment, wherein type K is of the formula: CF (compact flash)3CF2CF2O[CF(CF3)CF2O]nCF(CF3) COF, wherein n is a natural number greater than or equal to 1.
A hydrophobic and oleophobic coating in accordance with an embodiment, wherein type K has the formula:
wherein n is a natural number greater than or equal to 1.
A hydrophobic and oleophobic coating in accordance with an embodiment, wherein type Y is: CF (compact flash)3O(C3F6O)m(CF2O)nCF3M is a natural number of 1 or more, and n is a natural number of 1 or more.
The hydrophobic and oleophobic coating according to one embodiment, wherein the Y-type structure is:
wherein m is a natural number greater than or equal to 1, and n is a natural number greater than or equal to 1.
The hydrophobic and oleophobic coating of one embodiment, wherein Z-typingThe subformula is: CF (compact flash)3O(C2F4O)m(CF2O)nCF3Wherein m is a natural number greater than or equal to 1, and n is a natural number greater than or equal to 1.
According to one embodiment, the hydrophobic and oleophobic coating is characterized in that Z-type structure is
Wherein m is a natural number greater than or equal to 1, and n is a natural number greater than or equal to 1.
A hydrophobic and oleophobic coating according to one embodiment, wherein type D is of the formula: c3F7O(CF2CF2CF2O)nC2F5Wherein n is a natural number greater than or equal to 1.
A hydrophobic and oleophobic coating according to one embodiment, wherein type D is of the formula:
wherein n is a natural number greater than or equal to 1.
According to one embodiment, the hydrophobic oleophobic coating is characterized in that the perfluoropolyether has a formula
X1-O(CFXO)n(CFXCFXO)m(CF2CF2CF2O)p(CF2CF2CF2CF2O)q-X2(I) wherein-X1，X2Independently selected from the structural formula- (CF)2)ZCF3And CF (CF)3) COF, wherein z is an integer from 0 to 3; x is the same or different at each occurrence and is independently F or CF3N is an integer from 0 to 200; m is an integer from 0 to 200; p, q are integers from 0 to 100; p + q + m + n > 0, the average molecular weight of (I) being between 200 and 10000.
According to a principleThe hydrophobic and oleophobic coating of example (b), wherein the perfluoropolyether derivative is a perfluoropolyether hydroxyl derivative having at least one hydroxyl group (PFPE-OH), the derivative PFPE-OH conforming to formula T1-O-Rf-T2Wherein Rf is a fluoropolyoxyalkylene chain, T1And T2Are the same or different from each other and are independently selected from the formula-CF2CH2O(CH2CH2O) s' H and-CF2CF2CH2O(CH2CH2O) s ' H, wherein s ' and s ' are integers from 0 to 5.
The hydrophobic and oleophobic coating according to an embodiment, wherein the fluoropolyoxyalkene chain Rf of the derivative PFPE-OH is a chain comprising a recurring unit R ° selected from: (i) -CFXO-, wherein X is F or CF3(ii) -CFXCFXO-, wherein X is the same or different at each occurrence F or CF3With the proviso that at least one X is-F, (iii) -CF2CF2CF2O-，(iv)-CF2CF2CF2CF2O-，(v) -(CF2)j-CFZ-O-, wherein j is an integer from 0 to 3 and Z is a compound having the formula-O Rf' T3Wherein Rf' is a fluoropolyoxyalkylene chain comprising a number of repeating units from 0 to 10, T3Is C1-C3A perfluoroalkyl group.
The hydrophobic oleophobic coating according to one embodiment, wherein the repeating units R ° in Rf' are selected from the group consisting of: -CFXO-, -CF2CFXO-、-CF2CF2CF2O-、-CF2CF2CF2CF2O-, each X is independently F or CF3。
The hydrophobic and oleophobic coating according to one embodiment, wherein the perfluoropolyether or perfluoropolyether derivative is selected from SOLVAY
MD 700、
D、
E10H、
PEG 45、
SV 55、
HT 170、
SV 80 RP06、
Y L-VAC 16/6、
Y、
M100, or a mixture of a plurality of the above products.
The hydrophobic and oleophobic coating according to one embodiment, wherein the perfluoropolyether or perfluoropolyether derivative is Novec fluorinated liquid from 3M company or a mixture of one or more products containing the perfluoropolyether or perfluoropolyether derivative.
The hydrophobic and oleophobic coating according to one embodiment, wherein the perfluoropolyether derivative is a perfluoropolyether having at least one hydroxyl group or a perfluoropolyether having at least one carboxyl or ester group.
The hydrophobic and oleophobic coating in accordance with an embodiment, wherein the vapor deposition temperature range is 30-60 degrees.
The invention also provides a preparation method of the hydrophobic and oleophobic coating, which comprises the step of taking perfluoropolyether or perfluoropolyether derivatives as raw materials and forming the perfluoropolyether or perfluoropolyether derivatives on the surface of the substrate through vapor deposition in a PECVD mode.
A method of making a hydrophobic and oleophobic coating in accordance with an embodiment, wherein the perfluoropolyether derivative is a perfluoropolyether having at least one hydroxyl group or a perfluoropolyether having at least one carboxyl or ester group.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art. The basic principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
It is to be understood that the terms "a" and "an" are to be interpreted as meaning that a number of one element may be one in one embodiment or multiple in another embodiment, and the terms "a" and "an" are not to be interpreted as limiting the number.
References to "one embodiment," "an embodiment," "example embodiment," "various embodiments," "some embodiments," etc., indicate that the embodiment described herein may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the feature, structure, or characteristic. In addition, some embodiments may have some, all, or none of the features described for other embodiments.
The invention discloses a hydrophobic and oleophobic coating which can be formed on the surface of a substrate in a Plasma Enhanced Chemical Vapor Deposition (PECVD) mode. The hydrophobic and oleophobic coating can improve the water and oil resistance of the surface of the substrate.
Preferably, in the preparation of the hydrophobic and oleophobic coating, plasma vapor deposition is performed by using an inert gas as a gas source, such as but not limited to argon gas and helium gas, that is, the inert gas is used as a pretreatment gas or a plasma source gas.
Preferably, when the hydrophobic and oleophobic coating is prepared, a bias power supply, a radio frequency power supply or a microwave power supply is adopted as a power supply for vacuum coating, and optionally, the two or three can be combined.
Preferably, when the hydrophobic and oleophobic coating is prepared, the raw material used for the hydrophobic and oleophobic coating is perfluoropolyether or a perfluoropolyether derivative.
Further, the structural formula of the perfluoropolyether comprises K type, Y type, Z type and D type structures.
The molecular formula of the K type is as follows: CF (compact flash)3CF2CF2O[CF(CF3)CF2O]nCF(CF3)COF
The structural formula of the K type is as follows:
the Y-type molecular formula is: CF (compact flash)3O(C3F6O)m(CF2O)nCF3
The Y-type structural formula is:
the molecular formula of Z type is: CF (compact flash)3O(C2F4O)m(CF2O)nCF3
The Z-type structural formula is:
the molecular formula of the type D is: c3F7O(CF2CF2CF2O)nC2F5
The structural formula of the D form is as follows:
wherein m and n are natural numbers greater than or equal to 1.
The perfluoropolyether can also have the following structural formula
X1-O(CFXO)n(CFXCFXO)m(CF2CF2CF2O)p(CF2CF2CF2CF2O)q-X2(I) wherein-X1，X2Independently selected from the structural formula- (CF)2)ZCF3And CF (CF)3) COF, wherein z is an integer from 0 to 3; x is the same or different at each occurrence and is independently F or CF3N is an integer from 0 to 200; m is an integer from 0 to 200; p, q are integers from 0 to 100; p + q + m + n > 0, the average molecular weight of (I) being between 200 and 10000.
Further, the perfluoropolyether derivative is a perfluoropolyether hydroxyl derivative having at least one hydroxyl group (PFPE-OH), said derivative PFPE-OH conforming to formula T1-O-Rf-T2Wherein Rf is a fluoropolyoxyalkylene chain, T1And T2Are the same or different from each other and are independently selected from the formula-CF2CH2O(CH2CH2O) s' H and-CF2CF2CH2O(CH2CH2O) s ' H, wherein s ' and s ' are integers from 0 to 5.
The fluoropolyoxyalkylene chain Rf of the derivative PFPE-OH is a chain comprising a recurring unit R ° selected from:
(i) -CFXO-, wherein X is F or CF3，
(ii) -CFXCFXO-, wherein X, the same or different at each occurrence, is F or CF3Provided that at least one X is F,
(iii)-CF2CF2CF2O-，
(iv)-CF2CF2CF2CF2O-，
(v)-(CF2)j-CFZ-O-, wherein j is an integer from 0 to 3, and Z is a compound having the formula-O Rf' T3Of (2) aWherein Rf 'is a fluoropolyoxyalkylene chain comprising a number of repeating units from 0 to 10, said repeating units in Rf' being selected from the group consisting of: -CFXO-, -CF2CFXO-、-CF2CF2CF2O-、 -CF2CF2CF2CF2O-, wherein each X is independently F or CF3(ii) a And T3Is C1-C3A perfluoroalkyl group.
Further, the perfluoropolyether derivative can be an amorphous perfluorinated homopolymer or copolymer of perfluorodioxole. Wherein R' f is equal to RF or ORF, wherein RF is a linear or branched perfluoroalkyl group containing 1-5 carbon atoms; x1And X2The two being the same or different is F, CF3。
The mono/dicarboxylic perfluoropolyethers having acid and/or ester functional groups are of the formula A-O- (RF)z-(CFY)t-C(O)OX(II)，
Wherein X is H, C1-C10An alkyl or aryl group;
Y＝F、CF3；
t is 1, 2 or 3;
a is C1-C4Perfluoroalkyl end groups or C (O) OX;
z is 0 or 1; RF is a perfluorooxyalkylene chain comprising one or more of the following units in statistical distribution along the backbone: (C)3F6O); (CFYO) wherein Y is F or CF3；(CF2CF2O)；(CF2CF2CF2CF2O) having a number average molecular weight in the range of 180-.
Further, the perfluoropolyether derivative may be a perfluoropolyether having at least one hydroxyl group or a perfluoropolyether having at least one carboxyl group or ester group.
It is worth mentioning that the hydrophobic and oleophobic coating is formed by depositing perfluoropolyether or perfluoropolyether derivatives on the surface of the substrate by a low-temperature plasma chemical vapor deposition method to form the coating with hydrophobic and oleophobic properties. For example, the temperature in the chamber during chemical vapor deposition may be in the range of 30-60 degrees, which is more suitable for protecting the substrate from high temperature damage.
It is worth mentioning that the hydrophobic and oleophobic coating has a hydrophobic angle of over 100 degrees and a n-hexadecane oil repellency angle of over 60 degrees on the glass product. Can be used for glass, mobile phone screens, electronic products, medical instruments, clothes and fabrics and used as a hydrophobic oil-repellent layer or an anti-fingerprint layer.
The agent for the coating may be selected from SOLVAY
MD 700、 
D、
E10H、
PEG 45、
SV 55、 
HT 170、
SV 80RP06、
Y L-VAC 16/6、
Y、 
Novec fluorinated liquid from M100 or 3M company, or a mixture of a plurality of products containing perfluoropolyether or perfluoropolyether derivatives.
According to an embodiment of the present invention, the process for preparing the hydrophobic and oleophobic coating can be: (1) placing the substrate with a clean surface in a reaction chamber of plasma equipment, continuously vacuumizing the reaction chamber, and pumping the vacuum degree in the reaction chamber to 1-200 mTorr; (2) carrying out chemical vapor deposition on a substrate to prepare a film layer: (a) introducing a plasma source gas (such as inert gas including helium, argon and the like), starting pretreatment, and pretreating the base material by using plasma discharge, wherein the plasma is generated in the cavity by adopting means of radio frequency discharge, microwave or pulse discharge and the like. The monomer of the reaction raw material and the plasma source gas can be introduced simultaneously, or the matrix can be pretreated for 1-1800s after the plasma source gas is introduced, and then the reaction raw material monomer is introduced according to the requirements of the process parameters; (b) setting the pressure and temperature in a vacuum reaction chamber, simultaneously introducing gaseous or vaporized reaction raw material monomers, starting plasma discharge for deposition to perform plasma chemical vapor deposition, adjusting the plasma generation power to 300-500W, adjusting the temperature in the chamber to 30-60 ℃, stopping introducing the reaction raw material monomer gases after the reaction is finished, and increasing the pressure in the chamber to normal pressure. It is to be noted that, preferably, the plasma discharge for pretreatment and the plasma discharge for deposition are both performed by a pulsed bias power supply in a constant power mode.
Further, when the hydrophobic and oleophobic coating is prepared, the adopted process conditions are as follows: the discharge power supply adopts a constant power mode pulse bias power supply, the flow rate of a plasma source gas is 10-500sccm, the pressure is constant at 10-200mT, the monomer flow rate is 10-1000ul/min, the coating power is 400-500W, the frequency is 2KHz-70KHz, and the duty ratio is 5% -80%.
Example 1
Putting the glass wiped by the alcohol into a reaction cavity of a plasma chamber, and continuously vacuumizing the reaction cavity to ensure that the vacuum degree reaches 20 mTorr; introducing helium gas as a plasma source gas, wherein the flow rate is 50sccm, the temperature in the cavity is 55 ℃, starting plasma discharge to pretreat the base material, and the discharge power supply adopts a pulse bias power supply in a constant power mode, the power is 500W, the pulse frequency is 50KHz, the duty ratio is 10%, and the discharge time is 30 minutes.
And then, vaporizing the monomer raw material and introducing the vaporized monomer raw material into a reaction cavity, wherein the temperature inside the cavity is 45 ℃, the vaporization temperature of the monomer is 90 ℃, the helium flow is 50sccm, the pressure is constant at 80 mTorr, the monomer flow is 350ul/min, the coating stage is pulse discharge, a pulse bias power supply is adopted by a discharge power supply in a constant power mode, the power is 400W, the pulse frequency is 50KHz, the duty ratio is 10%, and the discharge time in the coating stage is 160 seconds.
The monomer raw materials are respectively obtained from SOLVAY company
Y、
D、 
MD 700、
HT 170 and
PEG 45. The hydrophobic and oleophobic angles measured after the coating were finished are shown in Table 1, and the oleophobic angle was measured using n-hexadecane.
TABLE 1
Example 2
Putting the watch band made of nylon into a reaction cavity of a plasma chamber, and continuously vacuumizing the reaction cavity to ensure that the vacuum degree reaches 20 mTorr; introducing helium gas as a plasma source gas, wherein the flow rate is 50sccm, the internal temperature of the cavity is 55 ℃, starting plasma discharge to pretreat the substrate, and the discharge power supply adopts a pulse bias power supply in a constant power mode, the power is 500W, the pulse frequency is 50KHz, the duty ratio is 10%, and the discharge time is 30 minutes.
Followed by monomer feed
HT 170 is vaporized and then is led into a reaction cavity, the temperature inside the cavity is 50 ℃, the monomer vaporization temperature is 100 ℃, the helium flow is 50sccm, the pressure is constant at 80 mTorr, the monomer flow is 300ul/min, the coating stage is pulse discharge, a pulse bias power supply is adopted by a discharge power supply in a constant power mode, the power is 450W, the pulse frequency is 50KHz, the duty ratio is 20%, and the coating stage time is 160 seconds.
After the coating, the hydrophobic angle was measured to be 132 °, and the hydrophobic angle was measured to be 93 ° using n-hexadecane.
Example 3
Putting the glass wiped by the alcohol into a vacuum coating cavity, and continuously vacuumizing the reaction cavity to enable the vacuum degree to reach 80 mTorr; introducing helium gas as a plasma source gas, wherein the flow rate is 50sccm, the internal temperature of the cavity is 55 ℃, starting plasma discharge to pretreat the substrate, and the discharge power supply adopts a pulse bias power supply in a constant power mode, the power is 500W, the pulse frequency is 50KHz, the duty ratio is 10%, and the discharge time is 30 minutes.
Subsequent dihydroxy perfluoropolyether derivatives starting with monomers
D and perfluoropolyethers
HT 170 mixes the obtained solution according to different mass ratios, gasifies after mixing, and introduces into a reaction cavity after gasifying, the temperature inside the cavity is 45 ℃, the monomer vaporization temperature is 90 ℃, the helium flow is 50sccm, the pressure is constant at 80 mTorr, the monomer flow is 400ul/min, the coating stage is pulse discharge, the discharge power supply adopts a pulse bias power supply in a constant power mode, the power is 460W, the pulse frequency is 50KHz, the duty ratio is 20%, and the coating stage time is 160 seconds.
The raw materials are mixed according to the proportion shown in the table, and the hydrophobic angle and the oleophobic angle are measured after the film coating is finished and are shown in the table 2, wherein the oil repellent angle is measured by using n-hexadecane.
TABLE 2
| Amount percentage of dihydroxyperfluoropolyether derivative substance (%) | Angle of hydrophobic (°) | Oil repelling Angle (°) |
| 85 | 106 | 62 |
| 65 | 108 | 63 |
| 50 | 110 | 63 |
| 35 | 115 | 65 |
| 25 | 110 | 64 |
It should be noted that in the above embodiments, glass and nylon watchbands are taken as examples of the substrate, but in other embodiments, other products or materials may also be taken as the substrate, and the composite film with a multilayer structure may be applied to different types of substrates, such as glass with a dense material surface, a mobile phone screen, an electronic product, a medical apparatus, a garment fabric, a fabric, and the like, as a hydrophobic oil-repellent layer or an anti-fingerprint layer, which is not limited in this respect.
It is also worth mentioning that in the prior art, the perfluoropolyether or the perfluoropolyether derivative is heated and dried after being impregnated to form a film layer on the surface of the substrate, the process is relatively complex and easily damages the substrate, and in the technical scheme of the application, the perfluoropolyether or the perfluoropolyether derivative is subjected to low-temperature vapor deposition on the surface of the substrate by a plasma vapor deposition technology to form the film layer, so that the manufacturing process is simpler, the substrate material is protected, and good hydrophobic and oleophobic performances of the raw material during film forming are maintained.
It will be appreciated by persons skilled in the art that the embodiments of the invention shown in the foregoing description are by way of example only and are not limiting of the invention. The objects of the invention have been fully and effectively accomplished. The functional and structural principles of the present invention have been shown and described in the examples, and any variations or modifications of the embodiments of the present invention may be made without departing from the principles described.
Claims (21)
1. A hydrophobic and oleophobic coating, comprising: and depositing perfluoropolyether or perfluoropolyether derivatives on the surface of a substrate in a PECVD (plasma enhanced chemical vapor deposition) mode to form the hydrophobic and oleophobic coating.
2. The hydrophobic and oleophobic coating of claim 1, wherein perfluoropolyether structures include K-type, Y-type, Z-type, D-type structures.
3. The hydrophobic and oleophobic coating of claim 1, wherein perfluoropolyether structural formula comprises a type K structure having the formula: CF (compact flash)3CF2CF2O[CF(CF3)CF2O]nCF(CF3) COF, wherein n is a natural number greater than or equal to 1.
4. The hydrophobic and oleophobic coating of claim 1, wherein the perfluoropolyether structure comprises a K-type structure, wherein the structure of K-type is:
wherein n is a natural number greater than or equal to 1.
5. The hydrophobic and oleophobic coating of claim 1, wherein perfluoropolyether structure formula comprises a Y-type structure having the formula: CF (compact flash)3O(C3F6O)m(CF2O)nCF3M is a natural number of 1 or more, and n is a natural number of 1 or more.
6. The hydrophobic and oleophobic coating of claim 1, wherein perfluoropolyether structure comprises a Y-type structure having the formula:
wherein m is a natural number greater than or equal to 1, and n is a natural number greater than or equal to 1.
7. The hydrophobic and oleophobic coating of claim 1, wherein perfluoropolyether structural formula comprises a Z-type structure having the formula: CF (compact flash)3O(C2F4O)m(CF2O)nCF3Wherein m is a natural number greater than or equal to 1, and n is a natural number greater than or equal to 1.
8. The hydrophobic and oleophobic coating of claim 1, wherein the perfluoropolyether structure comprises a Z-type structure having a formula of
Wherein m is a natural number greater than or equal to 1, and n is a natural number greater than or equal to 1.
9. The hydrophobic and oleophobic coating of claim 1, wherein perfluoropolyether structure formula comprises a type D structure having the formula: c3F7O(CF2CF2CF2O)nC2F5Wherein n is a natural number greater than or equal to 1.
10. The hydrophobic and oleophobic coating of claim 1, wherein perfluoropolyether structure formula comprises a type D structure having the formula:
wherein n is a natural number greater than or equal to 1.
11. The hydrophobic and oleophobic coating of claim 1, wherein said perfluoropolyether has formula X1-O(CFXO)n(CFXCFXO)m(CF2CF2CF2O)p(CF2CF2CF2CF2O)q-X2(I) wherein-X1，X2Independently selected from the structural formula- (CF)2)ZCF3And CF (CF)3) COF, wherein z is an integer from 0 to 3; x is the same or different at each occurrence and is independently F or CF3N is an integer from 0 to 200; m is an integer from 0 to 200; p, q are integers from 0 to 100; p + q + m + n > 0, the average molecular weight of (I) being between 200 and 10000.
12. The hydrophobic and oleophobic coating of claim 1, wherein the perfluoropolyether derivative is a perfluoropolyether hydroxyl derivative having at least one hydroxyl groupA compound (PFPE-OH), the derivative PFPE-OH corresponding to the formula T1-O-Rf-T2Wherein Rf is a fluoropolyoxyalkylene chain, T1And T2Are the same or different from each other and are independently selected from the formula-CF2CH2O(CH2CH2O) s' H and-CF2CF2CH2O(CH2CH2O) s ' H, wherein s ' and s ' are integers from 0 to 5.
13. The hydrophobic and oleophobic coating according to claim 12, wherein fluoropolyoxyalkylene chain Rf of said derivative PFPE-OH is a chain comprising a repeating unit R °, said repeating unit R ° being selected from: (i) -CFXO-, wherein X is F or CF3(ii) -CFXCFXO-, wherein X is the same or different at each occurrence F or CF3With the proviso that at least one X is-F, (iii) -CF2CF2CF2O-，(iv)-CF2CF2CF2CF2O-，(v)-(CF2)j-CFZ-O-, wherein j is an integer from 0 to 3 and Z is a compound having the formula-O Rf' T3Wherein Rf' is a fluoropolyoxyalkylene chain comprising a number of repeating units from 0 to 10, T3Is C1-C3A perfluoroalkyl group.
14. The hydrophobic oleophobic coating of claim 13, wherein the repeating units in Rf' are selected from the group consisting of: -CFXO-, -CF2CFXO-、-CF2CF2CF2O-、-CF2CF2CF2CF2O-, each X is independently F or CF3。
15. The hydrophobic and oleophobic coating of claim 1, wherein the perfluoropolyether derivative is a perfluoropolyether having at least one hydroxyl group or a perfluoropolyether having at least one carboxyl or ester group.
16. The hydrophobic and oleophobic coating of claim 1, wherein the vapor deposition temperature range is 30-60 degrees.
17. The preparation method of the hydrophobic and oleophobic coating is characterized in that perfluoropolyether or perfluoropolyether derivatives are used as raw materials and are formed on the surface of a substrate through vapor deposition in a PECVD mode.
18. A method of making a hydrophobic and oleophobic coating according to claim 17, wherein the perfluoropolyether derivative is a perfluoropolyether having at least one hydroxyl group or a perfluoropolyether having at least one carboxyl or ester group.
19. The method for preparing a hydrophobic and oleophobic coating according to claim 17, wherein the process for preparing said hydrophobic and oleophobic coating is: (1) placing the substrate in a reaction cavity of a plasma chamber, and pumping the vacuum degree in the reaction cavity to 10-200 mTorr; (2) introducing a plasma source gas, starting plasma discharge for pretreatment to pretreat the base material, (3) introducing a reaction raw material monomer into a reaction cavity after vaporization, and starting plasma discharge for deposition to perform chemical vapor deposition reaction; (4) and closing the plasma discharge for deposition, introducing clean compressed air or inert gas to return to normal pressure, opening the cavity and taking out the substrate.
20. The method for preparing the hydrophobic and oleophobic coating according to claim 19, wherein the reactant monomers can be introduced simultaneously with the plasma source gas, or the substrate is pretreated for 1-1800s after the plasma source gas is introduced, and then the reactant monomers are introduced.
21. The method of making a hydrophobic and oleophobic coating according to claim 19, wherein both the pre-treatment plasma discharge and the deposition plasma discharge are performed by a pulsed bias power supply in constant power mode.
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| CN202010766901.7A CN114059045A (en) | 2020-08-03 | 2020-08-03 | Hydrophobic and oleophobic coating, preparation method and product thereof |
| TW110128600A TWI769036B (en) | 2020-08-03 | 2021-08-03 | Hydrophobic and oleophobic coating and preparation method and product thereof |
| JP2023507681A JP2023536937A (en) | 2020-08-03 | 2021-08-03 | Hydrophobic/oleophobic coating layer, manufacturing method thereof, and product |
| EP21854121.7A EP4190940A4 (en) | 2020-08-03 | 2021-08-03 | Hydrophobic and oleophobic coating, preparation method therefor, and product |
| PCT/CN2021/110275 WO2022028412A1 (en) | 2020-08-03 | 2021-08-03 | Hydrophobic and oleophobic coating, preparation method therefor, and product |
| US18/040,313 US20230313444A1 (en) | 2020-08-03 | 2021-08-03 | Hydrophobic and oleophobic coating, preparation method therefor, and product |
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