CN107936751B - Fluorinated composition for water-proofing and rust-proofing and its application - Google Patents
Fluorinated composition for water-proofing and rust-proofing and its application Download PDFInfo
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- CN107936751B CN107936751B CN201711372691.8A CN201711372691A CN107936751B CN 107936751 B CN107936751 B CN 107936751B CN 201711372691 A CN201711372691 A CN 201711372691A CN 107936751 B CN107936751 B CN 107936751B
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
The invention discloses aA fluorinated composition for water rust prevention and use thereof, comprising the following components: 1) a free radical reaction product A comprising at least a fluoro ester monomer, a non-fluorine-containing double bond-containing monomer containing a cyclic group or a tert-butyl group, and a compound containing both a phenyl group and a mercapto group; 2) hydrofluoroether solvents. The fluorine ester monomer has a general formula of CH2＝C(R1)COO‑Q‑RfWherein R is1Is H, halogen atom, hydrocarbyl, halogenated hydrocarbyl, Q is a divalent organic radical, R isfIs a polyfluoroalkyl or perfluoropolyether group. The fluorinated composition for water resistance and rust prevention can form a thin coating film with excellent water resistance and rust prevention performance on the surface of an electronic device on the premise of not influencing the service performance of the electronic device, and the coating film is easy to remove.
Description
Technical Field
The invention relates to the field of surface protection of base materials, in particular to a fluorinated composition for water resistance and rust prevention and application thereof.
Background
Micro cracks or gaps are easily formed in the use process of core parts of electronic devices such as semiconductor chips (especially under a pressure environment), and if impurities enter the electronic devices through the micro cracks or the gaps, abnormal current circulation can be caused to generate misoperation. Sputtering a metal or metal oxide coating on the surface of an electronic device can prevent the formation of microcracks or voids while blocking the entry of ionic impurities such as chloride and sodium ions. These sputtered layers are porous and have high surface energies and are susceptible to contamination by contaminants. When solvent-based cleaners are not used, soil is difficult to remove and most solvents are harmful to the environment. Both dirt and cleaning residues can adversely affect the desired properties of the coating.
For this reason, the sputtered layer needs to be protected. Conventionally, electronic components such as a printed circuit board are protected by coating the electronic components with a resin such as an acrylic resin, a polyurethane resin, or an epoxy resin. However, the protective layers can only function under a thicker coating, and defects such as bubbles are easy to generate; and the production efficiency is low because the coating and curing process is needed. In addition, along with the miniaturization of electronic and electric equipment, it is difficult to apply the resin coating layer on the surface of the electronic device in many cases.
As a method for imparting protective properties by a thin coating layer, a method is known in which a solution in which a polyfluoroalkyl group-containing polymer is dissolved in a nonflammable low boiling point solvent is applied to the surface of an electronic component, and the solvent is dried to form a coating film made of the polyfluoroalkyl group-containing polymer. The polyfluoroalkyl group-containing polymer has attracted attention for use in multifunctional mobile terminal devices because it can exhibit sufficient protective performance at a film thickness of 1 μm or less.
During the use of the electronic device, not only the corrosion of water vapor is prevented, but also the corrosion caused by other corrosive substances is prevented, and the sputtering metal layer is prevented from being corroded. However, the existing polymeric protectants containing polyfluoroalkyl groups still have to be improved in terms of rust prevention.
Disclosure of Invention
The invention aims to provide a fluorinated composition for water resistance and rust prevention and a technical scheme for application thereof aiming at the defects in the prior art, and the fluorinated composition can form a thin coating with excellent water resistance and rust prevention performance on the surface of an electronic device on the premise of not influencing the service performance of the electronic device.
In order to solve the technical problems, the invention adopts the following technical scheme:
a fluorinated composition for water-proofing and rust-proofing, characterized by containing the following components:
1) a free radical reaction product A comprising at least a fluoro ester monomer, a non-fluorine-containing double bond-containing monomer containing a cyclic group or a tert-butyl group, and a compound containing both a phenyl group and a mercapto group;
2) hydrofluoroether solvents;
the fluorine ester monomer has the general formula (I)
CH2＝C(R1)COO-Q-Rf(I)
Wherein R is1Is H, halogen atom, hydrocarbyl, halogenated hydrocarbyl, Q is a divalent organic radical, R isfIs polyfluoroalkyl or perA fluoropolyether group.
The reaction product A contains fluorine ester monomer as essential component for providing waterproof and antirust function, and non-fluorine double bond monomer containing cyclic group or tert-butyl group and compound containing both phenyl group and mercapto group as auxiliary components, but in the absence of the above components or , the obtained reaction product has waterproof and antirust performance reaching the use requirement.
Halogen atoms, e.g. fluorine, chlorine, bromine, hydrocarbon radicals, e.g. C1～10Alkyl, cycloalkyl, phenyl, benzyl, etc., haloalkyl such as trifluoromethane, etc. Divalent organic radicals such as (CH)2)n(n is an integer of 1 to 6) and CH2CH2N(CH3)SO2、CH2CH2N(CH2CH3)SO2、CH(CH3)CH2N(CH3)SO2、CH2CH2NH、N(CH3)CH2CH2NH, and the like. Polyfluoroalkyl radicals such as (CF)2)2CF3、CF(CF3)2、(CF2)3CF3、CF2CF(CF3)2、C(CF3)3、(CF2)4H、(CF2)2CF(CF3)2、(CF2)5CF3、(CF2)7CF3Etc.; perfluoropolyether groups such as CF (CF)3)[OCF2CF(CF3)]pOCF2CF2CF3、CF2[OCF2CF2]pOCF3、C(O)CF(CF3)(OCF2CF(CF3))pOC3F7、C(O)CF(OCF2CF2)pOCF3And p is 1 to 20 on average.
, 100 weight portions of the reaction product A contains at most 0.75 portion of compound containing phenyl and sulfhydryl, and at most 36 portions of monomer containing cyclic group or tert-butyl group and containing non-fluorine double bond, which is used as auxiliary component, and has defined synergistic effect with essential component to promote the water-proof and rust-proof effects of essential component, but when the amount is too high, the synergistic effect may be affected.
Preferably, R in the fluoro ester monomer represented by the formula (I)1Is H or methyl.
step (B), R in the fluoroester monomer represented by the formula (I)fIs a linear perfluoroalkyl group having 4 to 6 carbon atoms or a perfluoropolyether group having a molecular weight of 400 to 1500.
Such fluoro ester monomers are listed below: CH (CH)2＝CHCOOCH2CH2CF2CF2CF2CF3、CH2＝C(CH3)COOCH2CH2CF2CF2CF2CF3、CH2＝CHCOOCH2CH2CF2CF2CF2CF2CF2CF3、CH2＝C(CH3)COOCH2CH2CF2CF2CF2CF2CF2CF3、CH2＝CHCOOCH2CH2N(CH3)SO2CF2CF2CF2CF3、CH2＝C(CH3)COOCH2CH2N(CH3)SO2CF2CF2CF2CF3、CH2＝CHCOOCH2CH2N(CH3)SO2CF2CF2CF2CF2CF2CF3、CH2＝C(CH3)COOCH2CH2N(CH3)SO2CF2CF2CF2CF2CF2CF3、CH2＝C(CH3)COOCH2CH2N(CH2CH3)SO2CF2CF2CF2CF3、CH2＝CHCOOCH2PFPE、CH2＝C(CH3)COOCH2PFPE, wherein PFPE is a perfluoropolyether group with molecular weight of 400-1500.
The fluorine-free double bond-containing monomer having a cyclic group or a t-butyl group is preferably or or more kinds of a mixture of the fluorine-free double bond-containing monomer having a cyclic group or a t-butyl group and N-vinylpyrrolidone, and examples of the fluorine-free double bond-containing monomer having a cyclic group or a t-butyl group include cyclic alkyl (meth) acrylates (e.g., cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, methylcyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like, and derivatives thereof having a substituent group in the ring), tert-butyl methacrylate, vinyl t-butyl formate, vinyl benzoate, vinyl alkylbenzoate (e.g., vinyl t-butylbenzoate), N-vinylpyrrolidone, N-vinylcarbazole, and the like, and more preferably, the fluorine-containing monomer having a cyclic group or a mixture thereof is 6335 or more preferably a mixture of the fluorine-containing monomer having a cyclic group and N-vinylpyrrolidone, N-vinylcyclopyrazole, and the like.
Preferably, the compound containing both phenyl and mercapto is or or more than 2-mercaptobenzothiazole, phenethyl mercaptan and benzyl mercaptan.
, the hydrofluoroether solvent contains at least hydrofluoroethers derived from tetrafluoroethylene.
Preferably, the tetrafluoroethylene derived hydrofluoroether is HFE-347.
The tetrafluoroethylene derived hydrofluoroether is obtained by the addition reaction of tetrafluoroethylene and polyhydric alcohol, and has the following specific reaction formula:
polyol HO-R is exemplified by CH3OH、CF3CH2OH、CH3CH2OH、CH3CH2CH2OH、CH3CH(OH)CH3、CH3OCH2CH2OH、CH3CH2CH2CH2OH、(CH3)2CH2CH2OH、m-CH3-C6H4-OH、C6H5-CH2OH、HCF2CF2CH2From the polyol, a tetrafluoroethylene derived hydrofluoroether HFE-254 (CH) can be prepared3OCF2CF2H)、HFE-347(CF3CH2OCF2CF2H)、HFE-374(CH3CH2OCF2CF2H)、HFE-494n(CH3CH2CH2OCF2CF2H)、HFE-494i((CH3)2CHOCF2CF2H)、HFE-494e2(CH3OCH2CH2OCF2CF2H)、HFE-5114n(CH3(CH2)3OCF2CF2H)、HFE-5114i((CH3)2CHCH2OCF2CF2H)、HFE-894m(m-CH3C6H4OCF2CF2H)、HFE-894Bz(C6H5CH2OCF2CF2H)、HFE-458(HCF2CF2CH2OCF2CF2H) of HFE-347, HFE-494n and HFE-458 are preferable, and HFE-347 is more preferable.
The composition of the present invention may contain or more kinds of non-tetrafluoroethylene derived hydrofluoroethers such as nonafluorobutyl methyl ether, nonafluoroisobutyl methyl ether, nonafluorobutyl ethyl ether and nonafluoroisobutyl ethyl ether, in addition to the tetrafluoroethylene derived hydrofluoroether.
The fluorinated composition for waterproofing and rust prevention is applied to waterproofing and rust prevention treatment of electronic equipment.
The reaction product A in the fluorinated water-proofing and rust-proofing composition of the present invention is obtained by polymerizing a compound containing at least a fluorine ester monomer, a non-fluorine-containing double bond-containing monomer having a cyclic group or a t-butyl group, and both a phenyl group and a mercapto group in a free radical solution. The polymerization solvent is fluorine-containing solvent, especially hydrofluoroether solvent, which has good solubility for polymerization raw material and polymer solvent formed, and is convenient for free radical reaction to proceed smoothly.
As the polymerization initiator, a commonly used radical initiator can be used, and oil-soluble ones are preferable, and examples thereof include azo-type azobisisobutyronitrile, azobisisoheptonitrile, and the like, and peroxy-type benzoyl peroxide, benzoyl peroxide t-butyl ester, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like, but are not limited thereto. These initiators may be used alone or in combination of two or more. The amount of the initiator is not particularly limited, and is usually 0.02 to 7.5 parts by mass, preferably 0.15 to 3.5 parts by mass, per 100 parts by mass of the monomer.
The polymerization system preferably directly adopts hydrofluoroether as a polymerization solvent, and avoids the steps of evaporating the solvent and then replacing the solvent with the hydrofluoroether solvent after polymerization. The concentration of the monomer in the polymerization system is 8 to 60 wt%, preferably 20 to 50 wt%.
The polymerization temperature, the polymerization time and the like can be properly adjusted according to the boiling point of a used solvent, the type of an initiator, the type of a monomer and the like, the polymerization temperature is usually controlled to be 50-100 ℃, and the polymerization time is 4-24 h.
The concentration of the reaction product A in the fluorinated composition for water-proofing and rust-proofing of the present invention is not particularly limited, and is 0.01 to 35% by mass, preferably 0.1 to 10% by mass, based on the saturation concentration, and the fluorinated composition for water-proofing and rust-proofing can be obtained by directly performing polymerization reaction, or can be obtained by adding a suitable hydrofluoroether solvent after polymerization reaction and diluting to constant concentration.
The fluorinated composition for water-proofing and rust-proofing of the present invention is not particularly limited to a substrate to be treated, and is suitable for a metal substrate, a plastic substrate, a glass substrate, a ceramic substrate, and the like, and can form a coating film having excellent water-proofing properties on the surface of the substrate to be treated. However, the fluorinated composition for water-proofing and rust-proofing of the present invention is particularly suitable for water-proofing and rust-proofing treatment of electronic devices, particularly for water-proofing and rust-proofing treatment of electronic device parts, printed circuit boards, and the like which are liable to fail when exposed to water, or electronic parts which are liable to be affected by corrosion in the environment.
After the surface treatment of electronic devices and the like with the above-mentioned fluorinated composition for water-proofing and rust-proofing, the adhesion or invasion of water can be effectively inhibited, and the adhered water can be easily removed by a proper drying treatment, so that the trouble which may be caused by the contact with water can be greatly reduced. In addition, the corrosion of the metal on the electronic device caused by the contact of the metal with water, oxygen and the like can be prevented, and the performance of the device is further influenced.
The method for treating a substrate with the fluorinated composition for water-proofing and rust-proofing of the present invention is not particularly limited as long as the composition of the present invention can be brought into sufficient contact with the substrate to be treated, and the treatment can be carried out by a method such as dipping, spraying, brush coating, towel coating, spin coating, or the like. Depending on the substrate to be treated, the fluorinated water-and rust-proofing composition is usually diluted to a concentration of 0.1 to 10 wt%, preferably 0.15 to 4 wt%.
When the surface treatment is performed, the treatment temperature is not particularly limited, and may be usually room temperature. When dipping is used, the dipping time is selected according to the use requirements of different devices, and is usually between 1 second and 10 hours. When spraying is employed, the spraying speed and the number of times are not particularly limited either, and it is usually the case that a uniform coating film can be formed. And drying the treated base material at room temperature in the air.
In order to ensure the effect of the coating film and the durability of the coating film, it is preferable to clean the substrate to remove oil stains, impurities, and the like on the surface before treating the substrate with the fluorinated composition for water-proofing and rust-proofing of the present invention. The cleaning may employ acetone, isopropanol, hydrofluoroethers or hydrofluorocarbons. In addition, the substrate may optionally be pretreated by plasma, corona, or the like.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. the fluorinated composition for water-proofing and rust-proofing of the present invention can impart good water-proofing and rust-proofing properties to various substrates and has good durability.
2. The coating film formed from the fluorinated composition for water-proofing and rust-proofing of the present invention is also excellent in oil-proofing and resistance to attack by conventional solvents (e.g., ethyl acetate, acetone, etc.).
3. The fluorinated composition for water-proofing and rust-proofing of the present invention uses hydrofluoroether, especially tetrafluoroethylene-derived hydrofluoroether, as a solvent, and does not have adverse effects such as corrosion on a substrate when the substrate is treated.
4. The coating film formed from the fluorinated waterproof and antirust composition of the present invention can be removed in a hydrofluoroether solvent, and is convenient for use in places where temporary protection is required.
Drawings
The invention is further described with reference to the following drawings:
FIG. 1 is a schematic view showing the contact angle of the composition of example 6 after the treatment of the fluorinated waterproof and antirust composition of the present invention and its application;
FIG. 2 is a schematic illustration of the contact angle to water after cleaning the coating in accordance with the present invention;
FIG. 3 is a schematic illustration of the contact angle of an untreated substrate of the present invention to water.
Detailed Description
The fluorinated composition for water-proofing and rust-proofing of the present invention comprises the following components:
1) a free radical reaction product A comprising at least a fluoro ester monomer, a non-fluorine-containing double bond-containing monomer containing a cyclic group or a tert-butyl group, and a compound containing both a phenyl group and a mercapto group;
2) hydrofluoroether solvents;
the fluorine ester monomer has the general formula (I)
CH2＝C(R1)COO-Q-Rf(I)
Wherein R is1Is H, halogen atom, hydrocarbyl, halogenated hydrocarbyl, Q is a divalent organic radical, R isfIs a polyfluoroalkyl or perfluoropolyether group.
The reaction product A contains fluorine ester monomer as essential component for providing waterproof and antirust function, and non-fluorine double bond monomer containing cyclic group or tert-butyl group and compound containing both phenyl group and mercapto group as auxiliary components, but in the absence of the above components or , the obtained reaction product has waterproof and antirust performance reaching the use requirement.
Halogen atoms, e.g. fluorine, chlorine, bromine, hydrocarbon radicals, e.g. C1～10Alkyl, cycloalkyl, phenyl, benzyl, etc., haloalkyl such as trifluoromethane, etc. Divalent organic radicals such as (CH)2)n(n is an integer of 1 to 6) and CH2CH2N(CH3)SO2、CH2CH2N(CH2CH3)SO2、CH(CH3)CH2N(CH3)SO2、CH2CH2NH、N(CH3)CH2CH2NH, and the like. Polyfluoroalkyl radicals such as (CF)2)2CF3、CF(CF3)2、(CF2)3CF3、CF2CF(CF3)2、C(CF3)3、(CF2)4H、(CF2)2CF(CF3)2、(CF2)5CF3、(CF2)7CF3Etc.; perfluoropolyether groups such as CF (CF)3)[OCF2CF(CF3)]pOCF2CF2CF3、CF2[OCF2CF2]pOCF3、C(O)CF(CF3)(OCF2CF(CF3))pOC3F7、C(O)CF(OCF2CF2)pOCF3And p is 1 to 20 on average.
100 parts by weight of the reaction product A contains at most 0.75 part of a compound containing both phenyl and mercapto groups and at most 36 parts of a monomer containing a cyclic group or a tert-butyl group and containing no fluorine-containing double bond as an auxiliary component, and the auxiliary component has a synergistic effect of with the essential component, and can promote the water-proof and rust-proof effects of the essential component, but when the amount is too high, the synergistic effect may be adversely affected.
Preferably, R in the fluoro ester monomer represented by the formula (I)1Is H or methyl.
R in the fluoro ester monomer represented by the general formula (I)fIs a linear perfluoroalkyl group having 4 to 6 carbon atoms or a perfluoropolyether group having a molecular weight of 400 to 1500.
Such fluoro ester monomers are listed below: CH (CH)2＝CHCOOCH2CH2CF2CF2CF2CF3、CH2＝C(CH3)COOCH2CH2CF2CF2CF2CF3、CH2＝CHCOOCH2CH2CF2CF2CF2CF2CF2CF3、CH2＝C(CH3)COOCH2CH2CF2CF2CF2CF2CF2CF3、CH2＝CHCOOCH2CH2N(CH3)SO2CF2CF2CF2CF3、CH2＝C(CH3)COOCH2CH2N(CH3)SO2CF2CF2CF2CF3、CH2＝CHCOOCH2CH2N(CH3)SO2CF2CF2CF2CF2CF2CF3、CH2＝C(CH3)COOCH2CH2N(CH3)SO2CF2CF2CF2CF2CF2CF3、CH2＝C(CH3)COOCH2CH2N(CH2CH3)SO2CF2CF2CF2CF3、CH2＝CHCOOCH2PFPE、CH2＝C(CH3)COOCH2PFPE ofThe PFPE is a perfluoropolyether group with the molecular weight of 400-1500.
The fluorine-free double bond-containing monomer having a cyclic group or a t-butyl group is preferably or a mixture of or more of cycloalkyl acrylate, cycloalkyl methacrylate, t-butyl acrylate, t-butyl methacrylate and N-vinylpyrrolidone, and examples of the fluorine-free double bond-containing monomer having a cyclic group or a t-butyl group include cycloalkyl (meth) acrylate (e.g., cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, methylcyclopentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and derivatives thereof having a substituent on the ring), t-butyl methacrylate, vinyl tert-butyl formate, vinyl benzoate, vinyl alkylbenzoate (e.g., vinyl tert-butylbenzoate), N-vinylpyrrolidone, N-vinylcarbazole, and the like, and more preferably, the fluorine-free double bond-containing monomer having a cyclic group or a t-butyl group is 6335 or more than t-butyl methacrylate, vinyl pyrrolidone, N-vinylpyrrolidone, N-vinylpyrrolidone, and the mixture thereof.
Preferably, the compound containing both phenyl and mercapto is or or more than 2-mercaptobenzothiazole, phenethyl mercaptan and benzyl mercaptan.
The hydrofluoroether solvent contains at least hydrofluoroethers derived from tetrafluoroethylene.
Preferably, the tetrafluoroethylene derived hydrofluoroether is HFE-347.
The tetrafluoroethylene derived hydrofluoroether is obtained by the addition reaction of tetrafluoroethylene and polyhydric alcohol, and has the following specific reaction formula:
polyol HO-R is exemplified by CH3OH、CF3CH2OH、CH3CH2OH、CH3CH2CH2OH、CH3CH(OH)CH3、CH3OCH2CH2OH、CH3CH2CH2CH2OH、(CH3)2CH2CH2OH、m-CH3-C6H4-OH、C6H5-CH2OH、HCF2CF2CH2From the polyol, a tetrafluoroethylene derived hydrofluoroether HFE-254 (CH) can be prepared3OCF2CF2H)、HFE-347(CF3CH2OCF2CF2H)、HFE-374(CH3CH2OCF2CF2H)、HFE-494n(CH3CH2CH2OCF2CF2H)、HFE-494i((CH3)2CHOCF2CF2H)、HFE-494e2(CH3OCH2CH2OCF2CF2H)、HFE-5114n(CH3(CH2)3OCF2CF2H)、HFE-5114i((CH3)2CHCH2OCF2CF2H)、HFE-894m(m-CH3C6H4OCF2CF2H)、HFE-894Bz(C6H5CH2OCF2CF2H)、HFE-458(HCF2CF2CH2OCF2CF2H) of HFE-347, HFE-494n and HFE-458 are preferable, and HFE-347 is more preferable.
The composition of the present invention may contain or more kinds of non-tetrafluoroethylene derived hydrofluoroethers such as nonafluorobutyl methyl ether, nonafluoroisobutyl methyl ether, nonafluorobutyl ethyl ether and nonafluoroisobutyl ethyl ether, in addition to the tetrafluoroethylene derived hydrofluoroether.
The fluorinated composition for waterproofing and rust prevention is applied to waterproofing and rust prevention treatment of electronic equipment.
The reaction product A in the fluorinated water-proofing and rust-proofing composition of the present invention is obtained by polymerizing a compound containing at least a fluorine ester monomer, a non-fluorine-containing double bond-containing monomer having a cyclic group or a t-butyl group, and both a phenyl group and a mercapto group in a free radical solution. The polymerization solvent is fluorine-containing solvent, especially hydrofluoroether solvent, which has good solubility for polymerization raw material and polymer solvent formed, and is convenient for free radical reaction to proceed smoothly.
As the polymerization initiator, a commonly used radical initiator can be used, and oil-soluble ones are preferable, and examples thereof include azo-type azobisisobutyronitrile, azobisisoheptonitrile, and the like, and peroxy-type benzoyl peroxide, benzoyl peroxide t-butyl ester, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like, but are not limited thereto. These initiators may be used alone or in combination of two or more. The amount of the initiator is not particularly limited, and is usually 0.02 to 7.5 parts by mass, preferably 0.15 to 3.5 parts by mass, per 100 parts by mass of the monomer.
The polymerization system preferably directly adopts hydrofluoroether as a polymerization solvent, and avoids the steps of evaporating the solvent and then replacing the solvent with the hydrofluoroether solvent after polymerization. The concentration of the monomer in the polymerization system is 8 to 60 wt%, preferably 20 to 50 wt%.
The polymerization temperature, the polymerization time and the like can be properly adjusted according to the boiling point of a used solvent, the type of an initiator, the type of a monomer and the like, the polymerization temperature is usually controlled to be 50-100 ℃, and the polymerization time is 4-24 h.
The concentration of the reaction product A in the fluorinated composition for water-proofing and rust-proofing of the present invention is not particularly limited, and is 0.01 to 35% by mass, preferably 0.1 to 10% by mass, based on the saturation concentration, and the fluorinated composition for water-proofing and rust-proofing can be obtained by directly performing polymerization reaction, or can be obtained by adding a suitable hydrofluoroether solvent after polymerization reaction and diluting to constant concentration.
The fluorinated composition for water-proofing and rust-proofing of the present invention is not particularly limited to a substrate to be treated, and is suitable for a metal substrate, a plastic substrate, a glass substrate, a ceramic substrate, and the like, and can form a coating film having excellent water-proofing properties on the surface of the substrate to be treated. However, the fluorinated composition for water-proofing and rust-proofing of the present invention is particularly suitable for water-proofing and rust-proofing treatment of electronic devices, particularly for water-proofing and rust-proofing treatment of electronic device parts, printed circuit boards, and the like which are liable to fail when exposed to water, or electronic parts which are liable to be affected by corrosion in the environment.
After the surface treatment of electronic devices and the like with the above-mentioned fluorinated composition for water-proofing and rust-proofing, the adhesion or invasion of water can be effectively inhibited, and the adhered water can be easily removed by a proper drying treatment, so that the trouble which may be caused by the contact with water can be greatly reduced. In addition, the corrosion of the metal on the electronic device caused by the contact of the metal with water, oxygen and the like can be prevented, and the performance of the device is further influenced.
The method for treating a substrate with the fluorinated composition for water-proofing and rust-proofing of the present invention is not particularly limited as long as the composition of the present invention can be brought into sufficient contact with the substrate to be treated, and the treatment can be carried out by a method such as dipping, spraying, brush coating, towel coating, spin coating, or the like. Depending on the substrate to be treated, the fluorinated water-and rust-proofing composition is usually diluted to a concentration of 0.1 to 10 wt%, preferably 0.15 to 4 wt%.
When the surface treatment is performed, the treatment temperature is not particularly limited, and may be usually room temperature. When dipping is used, the dipping time is selected according to the use requirements of different devices, and is usually between 1 second and 10 hours. When spraying is employed, the spraying speed and the number of times are not particularly limited either, and it is usually the case that a uniform coating film can be formed. And drying the treated base material at room temperature in the air.
In order to ensure the effect of the coating film and the durability of the coating film, it is preferable to clean the substrate to remove oil stains, impurities, and the like on the surface before treating the substrate with the fluorinated composition for water-proofing and rust-proofing of the present invention. The cleaning may employ acetone, isopropanol, hydrofluoroethers or hydrofluorocarbons. In addition, the substrate may optionally be pretreated by plasma, corona, or the like.
The raw materials used in the invention can be sold in the market or prepared, and are specifically as follows:
C4：CH2＝CHCOOCH2CH2CF2CF2CF2CF3(from Hengtong fluorochemicals)
C6：CH2＝C(CH3)COOCH2CH2CF2CF2CF2CF2CF2CF3(from Juhua group)
CF：CH2＝C(CH3)COOCH2CF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3(from methacrylic acid (available from Tuo Chemicals) and HOCH2CF(CF3)[OCF2CF(CF3)]pOCF2CF2CF3(from the Macro group) esterification reaction preparation, where P averages 5.3)
Tert-butyl methacrylate ( Qianji chemical Co., Ltd., city)
Cyclohexyl methacrylate (Nanjing hand-in-hand chemical technology, Inc.)
N-vinyl pyrrolidone ( Huao chemical Co., Ltd., city)
2-mercaptobenzothiazole (Suzhou fu lu Biotech Co., Ltd.)
Phenethyl mercaptan (Shanghai Yuyu new material science and technology Co., Ltd.)
Benzyl mercaptan (Jinan Luli chemical Co., Ltd.)
Azobisbutyronitrile (from Shanghai Hao chemical Co., Ltd.)
HFE-347 (from Juhua group)
Example 1
168.5g of C were placed in a 1L four-necked reaction flask equipped with a stirrer, a constant temperature oil bath, a thermometer and a condenser430g of tert-butyl methacrylate, 1g of phenethyl mercaptan, 0.5g of azobisbutyronitrile and 400g of HFE-347, and then heating and refluxing for reaction for 10 hours to obtain the fluorinated composition for water and oil proofing.
Examples 2 to 5
The same procedure as in example 1 was followed, and the detailed formulation is shown in Table 1.
TABLE 1
Examples 6 to 10
The same procedure was followed as in example 1, and the detailed formulation is shown in Table 2.
TABLE 2
Examples 11 to 12 and comparative examples 1 to 4
The same procedure was followed as in example 1, and the detailed formulation is shown in Table 3.
TABLE 3
Substrate processing method
The substrate was first cleaned with ethanol and then with HFE-347 to complete the pretreatment.
The water-proof and rust-proof fluorine-containing compositions obtained in examples 1 to 12 and comparative examples 1 to 4 were diluted with HFE-347 to a concentration of 0.2 wt%, sprayed on the surface of the pretreated substrate, and then dried at room temperature for 30 minutes to obtain test pieces.
Performance testing
(1) Contact Angle testing
And (3) carrying out contact angle test on the sample to be tested by using a contact angle tester for deionized water (W) and white mineral oil (O). The assay was performed 5 times in parallel and the mean value was taken. The results are detailed in Table 4.
(2) Salt spray resistance test
And (3) performing a salt spray resistance test on the treated base material by referring to GB/T2423.17-2008, wherein the specific test conditions are as follows: the spray solution is 5% sodium chloride solution, the pH value is 6.5-7.2, and the spray solution is controlled at 35 ℃. The results are detailed in Table 5.
Table 4 contact Angle test
Note: comparative example contact angle data could not be obtained due to severe tarnishing after 120h salt spray resistance.
TABLE 5 test of rust inhibitive performance
(3) Abrasion resistance test
The treated sample was measured for contact angle with water, and then placed on a tribometer, and surface rubbing was performed a predetermined number of times with a load of 100g, and then the contact angle with water was again measured. The results are detailed in Table 6.
| Number of rubs | Example 3 | Comparative example 2 |
| 0 | 105 | 105 |
| 15 | 100 | 85 |
| 30 | 95 | 73 |
TABLE 6 abrasion resistance test
(4) Removal performance determination
The treated substrate was placed in HFE-347 and then ultrasonically cleaned, after 30 minutes, removed. Whether the removal is possible or not is determined by the change in contact angle before and after cleaning. The results are shown in detail in FIGS. 1 to 3.
As can be seen from fig. 1 to 3, the contact angle to water after cleaning is similar to that of the untreated substrate, and the coating is removed.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple variations, equivalent substitutions or modifications based on the present invention to achieve substantially the same technical effects are within the scope of the present invention.
Claims (9)
1. A fluorinated composition for water-proofing and rust-proofing, characterized by containing the following components:
1) the free radical reaction product A at least comprises a fluorine ester monomer, a non-fluorine-containing double bond monomer containing a cyclic group or a tert-butyl group and a compound containing both phenyl and mercapto, wherein 100 parts by weight of the reaction product A contains at most 0.75 part of the compound containing both phenyl and mercapto and at most 36 parts of the non-fluorine-containing double bond monomer containing the cyclic group or the tert-butyl group;
2) hydrofluoroether solvents;
the fluorine ester monomer has a general formula (I) of
CH2＝C(R1)COO-Q-Rf(I)
Wherein R is1Is H, halogen atom, hydrocarbyl, halogenated hydrocarbyl, Q is a divalent organic radical, R isfIs a polyfluoroalkyl or perfluoropolyether group.
2. The fluorinated waterproof antirust composition according to claim 1, wherein: r in the fluorine ester monomer represented by the general formula (I)1Is H or methyl.
3. The fluorinated waterproof antirust composition according to claim 1, wherein: r in the fluorine ester monomer represented by the general formula (I)fIs a linear perfluoroalkyl group having 4 to 6 carbon atoms or a perfluoropolyether group having a molecular weight of 400 to 1500.
4. The fluorinated composition for water-proofing and rust-proofing according to claim 1, wherein said monomer having a cyclic group or a t-butyl group and containing no fluorine-containing double bond is or or more kinds selected from the group consisting of a cycloalkyl acrylate, a cycloalkyl methacrylate, a t-butyl acrylate, a t-butyl methacrylate and N-vinylpyrrolidone.
5. The fluorinated composition for water-proofing and rust-proofing according to claim 1 or 4, wherein the monomer having a cyclic group or a t-butyl group and containing no fluorine and a double bond is or a mixture of or more of cyclohexyl methacrylate, t-butyl methacrylate and N-vinylpyrrolidone.
6. The fluorinated waterproof and antirust composition according to claim 1, wherein the compound containing both said phenyl group and said mercapto group is or a mixture of or more of 2-mercaptobenzothiazole, phenethyl mercaptan and benzyl mercaptan.
7. The fluorinated waterproof/antirust composition according to claim 1, wherein the hydrofluoroether-based solvent contains at least types of tetrafluoroethylene-derived hydrofluoroethers.
8. The fluorinated waterproof antirust composition according to claim 7, wherein: the tetrafluoroethylene derived hydrofluoroether is HFE-347.
9. The fluorinated waterproof and antirust composition according to claim 1, which is applied to waterproof and antirust treatment of electronic equipment.
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