CN109897493A - A kind of three-proofing coating and preparation method thereof - Google Patents
A kind of three-proofing coating and preparation method thereof Download PDFInfo
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- CN109897493A CN109897493A CN201711296423.2A CN201711296423A CN109897493A CN 109897493 A CN109897493 A CN 109897493A CN 201711296423 A CN201711296423 A CN 201711296423A CN 109897493 A CN109897493 A CN 109897493A
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Abstract
The invention discloses a kind of three-proofing coatings and preparation method thereof.Wherein the three-proofing coating includes fluoropolymer and fluoride solvent；The fluoropolymer has structural unit shown in formula (I) and formula (II): wherein, X is hydrogen atom, alkyl or halogen atom with 1~3 carbon atom, Y is the aliphatic group with 1~3 carbon atom, and Rf is the perfluoroalkyl with 4~10 carbon atoms；A1For hydrogen atom, methyl or the halogen atom in addition to fluorine atom, A2For the alkyl with 1~10 carbon atom.The three-proofing coating is using the fluoropolymer of the perfluoroalkyl with 4~10 carbon atoms as bulk composition, using fluoride solvent as solvent, under the premise of with good Water-proof and oil-proof, anti-pollution and on product appearance without influence, it can form a film without baking, ultraviolet light solidification, use process is simple, at low cost.
Description
Technical field
The present invention relates to three-proofing coating technical field, in particular to a kind of three-proofing coating and preparation method thereof.
Background technique
Three-proofing coating is a kind of coating for being used for electronic component (such as printed circuit board) surfacecti proteon, so that electronics member device
Part surface has excellent waterproof performance, oil preventing performance and anti-pollution.
A kind of three-proofing coating mixed by various kinds of resin such as polyurethane, organosilicons is provided in the related technology, has been specifically included
Machine Si acrylate resin, polyurethane acrylate resin, reactive fluorinated diluent, not reactive fluorinated diluent, photoinitiator,
And the auxiliary agents such as levelling agent, drier, fluorescer.The three-proofing coating when in use, is first toasted after being coated on matrix,
Three proofings lacquer coat is formed after carrying out ultraviolet light solidification again.
In the implementation of the present invention, the inventors discovered that in the related technology the prior art has at least the following problems:
The three-proofing coating complicated component that the relevant technologies provide, and need that coating could be formed through overbaking, ultraviolet light solidification, make
It is complex with process, higher cost.
Summary of the invention
In order to solve the above technical problems, the embodiment of the present invention provides that a kind of ingredient is simple, use process is simple, cost
Low three-proofing coating and preparation method thereof.
Specifically, including technical solution below:
On the one hand, the embodiment of the invention provides a kind of three-proofing coating, the three-proofing coating includes fluoropolymer and fluorine-containing molten
Agent；
The fluoropolymer has structural unit shown in formula (I) and formula (II):
Wherein, X be hydrogen atom, alkyl or halogen atom with 1~3 carbon atom,
Y is the aliphatic group with 1~3 carbon atom,
Rf is the perfluoroalkyl with 4~10 carbon atoms；
Wherein, A1For hydrogen atom, methyl or the halogen atom in addition to fluorine atom,
A2For the alkyl with 1~10 carbon atom.
Optionally, the quantitative proportion of structural unit shown in formula (I) and structural unit shown in formula (II) are as follows: (1~10):
1。
Optionally, the fluoride solvent be selected from nona-fluoro butyl group ether, nona-fluoro butyl group methyl ether, 1,1,2,2- tetra- fluoro ethyl -2,
At least one of 2,2- trifluoroethyl ether and fluorocarbon solvent.
Optionally, in the three-proofing coating, the fluoropolymer-containing mass fraction is 1 part~10 parts, the fluoride solvent
Mass fraction be 30 parts~100 parts.
On the other hand, the embodiment of the invention provides a kind of preparation method of three-proofing coating, the preparation method includes:
Step S1 makes acrylate monomer shown in fluorochemical monomer and formula shown in formula (III) (IV) carry out radical polymerization
It closes reaction and obtains fluoropolymer；
Wherein, X be hydrogen atom, alkyl or halogen atom with 1~3 carbon atom,
Y is the aliphatic group with 1~3 carbon atom,
Rf is the perfluoroalkyl with 4~10 carbon atoms；
Wherein, A1For the halogen atom other than hydrogen atom, methyl or fluorine removal,
A2For the alkyl with 1~10 carbon atom；
The fluoropolymer and fluoride solvent are mixed to get the three-proofing coating by step S2.
Optionally, step S1 includes:
Step S11, by acrylate monomer, initiator and institute shown in fluorochemical monomer shown in formula (III), formula (IV)
State fluoride solvent be uniformly mixed obtain mixed solution；
The fluoride solvent is added into reaction vessel and is warming up to default temperature under inert gas protection by step S12
Degree；
The mixed solution is added dropwise in the reaction vessel by step S13, and preset time is reacted after being added dropwise and is obtained
The fluoropolymer.
Optionally, the mass fraction of fluorochemical monomer shown in formula (III) is 200 parts~1000 parts, third shown in formula (IV)
The mass fraction of olefin(e) acid ester monomer is 10 parts~40 parts, and the mass fraction of the initiator is 0.4 part~4 parts, and the mixing is molten
The gross mass number of the fluoride solvent in fluoride solvent and the reaction vessel in liquid is 500 parts~5000 parts.
Optionally, the fluoride solvent be selected from nona-fluoro butyl group ether, nona-fluoro butyl group methyl ether, 1,1,2,2- tetra- fluoro ethyl -2,
At least one of 2,2- trifluoroethyl ethers and fluorocarbon solvent, the preset temperature are 50 DEG C~100 DEG C.
Optionally, before step S11, the preparation method further include:
Successively fluorochemical monomer shown in formula (III) is washed using akaline liquid and water, using molecular sieve to washing
Fluorochemical monomer afterwards is dried, and is filtered to the fluorochemical monomer after drying.
Optionally, in step S2, the fluoropolymer-containing mass fraction is 1 part~10 parts, the matter of the fluoride solvent
Measuring number is 30 parts~100 parts；
Mixing temperature is 0 DEG C~25 DEG C, and incorporation time is 1 hour~2 hours.
Technical solution provided in an embodiment of the present invention the utility model has the advantages that
In three-proofing coating provided in an embodiment of the present invention, with the fluoropolymer of the perfluoroalkyl with 4~10 carbon atoms
As bulk composition, using fluoride solvent as solvent, the three-proofing coating is with good Water-proof and oil-proof, anti-pollution, and to production
Under the premise of product appearance is without influence, it is not required to add other auxiliary agents, can forms a film without baking, ultraviolet light solidification, ingredient is simple, makes
It is simple with process, it is at low cost.
The coating thickness of three-proofing coating provided in an embodiment of the present invention can achieve 100 nanometers~1000 nanometers.
Three-proofing coating provided in an embodiment of the present invention is applied widely, including but not limited to electronic circuit surface-assembled
The surfacecti proteon of (Surface Mount Technology, SMT) technique and various electronic components (such as integrated circuit)
Damp-proof insulation.
Specific embodiment
To keep technical solution of the present invention and advantage clearer, embodiment of the present invention is made below further detailed
Description.Unless otherwise defined, all technical terms used in the embodiment of the present invention all have usually manages with those skilled in the art
The identical meaning of solution.
On the one hand, the embodiment of the invention provides a kind of three-proofing coating, which includes fluoropolymer and fluoride solvent.
Wherein, fluoropolymer has structural unit shown in formula (I) and formula (II):
Wherein, X be hydrogen atom, alkyl or halogen atom with 1~3 carbon atom,
Y is the aliphatic group with 1~3 carbon atom,
Rf is the perfluoroalkyl with 4~10 carbon atoms；
Wherein, A1For hydrogen atom, methyl or the halogen atom in addition to fluorine atom,
A2For the alkyl with 1~10 carbon atom.
Three-proofing coating is coated in by component for forming a film based on fluoropolymer in three-proofing coating provided in an embodiment of the present invention
After matrix surface, after fluoride solvent volatilization, fluoropolymer forms a film in matrix surface, protects matrix surface.
In three-proofing coating provided in an embodiment of the present invention, by have the fluorine-containing poly- of the perfluoroalkyl of 4~10 carbon atoms
Object is closed as bulk composition, using fluoride solvent as solvent, so that the three-proofing coating is with good Water-proof and oil-proof, anti-pollution,
And it is colorless and transparent, do not influence product appearance under the premise of, be not required to add other auxiliary agents, can be at without baking, ultraviolet light solidification
Film, ingredient is simple, and use process is simple, at low cost.
In the embodiment of the present invention, in structural unit shown in formula (I), X concretely methyl, ethyl, n-propyl, isopropyl
Base, fluorine atom, chlorine atom, bromine atom or iodine atom.
Y concretely methylene, ethylidene, propylidene, Deng chlorine atom can be replaced fluorine atom, bromine atom, iodine atom etc..
Rf can be perfluor straight chained alkyl, or the positive fourth of the perfluoroalkyl with branch, including but not limited to perfluor
Base, perfluor n-pentyl, perfluor n-hexyl, perfluor n-heptyl, n-perfluoro-octyl, perfluor n-nonyl, perfluor positive decyl etc..
In structural unit shown in formula (II), A2Can be straight chained alkyl, for example, methyl, ethyl, n-propyl, normal-butyl,
N-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl etc., or the alkyl with branch, such as isopropyl
Base, isobutyl group, isopentyl, neopentyl etc..
It is understood that the fluoropolymer in three-proofing coating provided in an embodiment of the present invention generallys use free radical polymerization
Reaction is prepared, and therefore, without specific molecular structure, a kind of possible molecular structure is shown below:
Wherein, m, n and k are mutually independent integer, and m, n and k can be 1~100 integer.
In the embodiment of the present invention, in fluoropolymer, structural unit shown in formula (I) and structural unit shown in formula (II)
Quantitative proportion can be with are as follows: (1~10): 1, such as 1:1,2:1,3:1,4:1,5:1,6:1,7:1,8:1,9:1,10:1 etc..
Further, in three-proofing coating provided in an embodiment of the present invention, fluoride solvent can be nona-fluoro butyl group ether, nine fluorine fourths
At least one of base methyl ether, tetra- fluoro ethyl -2,2,2- trifluoroethyl ether of 1,1,2,2- and fluorocarbon solvent.
Further, in three-proofing coating provided in an embodiment of the present invention, the ratio of fluoropolymer and fluoride solvent can root
It is determined according to drying time needs, coating thickness needs etc..When needing to form thicker three proofings paint film, can suitably subtract
Few fluoride solvent dosage, to improve the viscosity of three-proofing coating, to improve coating thickness.By adjusting fluoropolymer with it is fluorine-containing molten
The ratio of agent can make the coating thickness of three-proofing coating reach 100 nanometers~1000 nanometers.In one possible implementation, contain
The mass fraction of fluoropolymer is 1 part~10 parts, such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts etc.,
The mass fraction of fluoride solvent can be 30 parts~100 parts, such as 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts,
100 parts etc..
On the other hand, the embodiment of the invention provides a kind of preparation method of three-proofing coating, it is used to prepare the embodiment of the present invention
The three-proofing coating of first aspect, the preparation method the following steps are included:
Step S1 makes acrylate monomer shown in fluorochemical monomer and formula shown in formula (III) (IV) carry out radical polymerization
It closes reaction and obtains fluoropolymer；
Wherein, X be hydrogen atom, alkyl or halogen atom with 1~3 carbon atom,
Y is the aliphatic group with 1~3 carbon atom,
Rf is the perfluoroalkyl with 4~10 carbon atoms；
Wherein, A1For the halogen atom other than hydrogen atom, methyl or fluorine removal,
A2For the alkyl with 1~10 carbon atom；
Fluoropolymer and fluoride solvent are mixed to get three-proofing coating by step S2.
The specific structure of X, Y and Rf can refer to above for X, Y in formula (I) in fluorochemical monomer shown in formula (III)
With the explanation of the specific structure of Rf, A in acrylate monomer shown in formula (IV)2Specific structure can refer to above for formula
(II) A in2Specific structure explanation, details are not described herein.
In preparation method provided in an embodiment of the present invention, step S1 may include:
Step S11 by acrylate monomer, initiator shown in fluorochemical monomer shown in formula (III), formula (IV) and contains
Fluorous solvent is uniformly mixed and obtains mixed solution；
Fluoride solvent is added into reaction vessel and is warming up to preset temperature under inert gas protection by step S12；
Step S13, mixed solution is added dropwise in reaction vessel, and preset time is reacted after being added dropwise and obtains fluoropolymer
Object.
Fluoride solvent used in the process of preparing fluoropolymer can be used identical with the fluoride solvent in three-proofing coating
Type.
In the preparation method that the embodiment of the present disclosure provides, the mass fraction of fluorochemical monomer shown in formula (III) can be 200
Part~1000 parts, such as 200 parts, 250 parts, 300 parts, 350 parts, 400 parts, 450 parts, 500 parts, 550 parts, 600 parts, 650 parts,
700 parts, 750 parts, 800 parts, 850 parts, 900 parts, 950 parts, 1000 parts etc.；The mass parts of acrylate monomer shown in formula (IV)
Number can be 10 parts~40 parts, such as 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts etc.；The mass fraction of initiator
It can be 0.4 part~4 parts, such as 0.4 part, 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts etc.；Mixed solution
In fluoride solvent and reaction vessel in fluoride solvent gross mass number can be 500 parts~5000 parts, such as 500 parts,
600 parts, 700 parts, 800 parts, 900 parts, 1000 parts, 1500 parts, 2000 parts, 2500 parts, 3000 parts, 3500 parts, 4000 parts, 4500
Part, 5000 parts etc..
In the embodiment of the present invention, the initiator for causing Raolical polymerizable can drawing for any Raolical polymerizable
Send out agent, including but not limited to azo-initiator and peroxide type initiators, wherein azo-initiator can be azo two
Perhaps the peroxide type initiators such as azobisisoheptonitrile can be benzoyl peroxide or benzoyl peroxide uncle to isobutyronitrile
Butyl ester etc..
In the embodiment of the present invention, fluoride solvent can be nona-fluoro butyl group ether, nona-fluoro butyl group methyl ether, 1,1,2,2- tetrafluoro second
Base -2,2, at least one of 2- trifluoroethyl ether and fluorocarbon solvent, correspondingly, the preset temperature in step S12 can be
50 DEG C~100 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C etc..
In the embodiment of the present invention, in step S12, inert gas can be this fields such as nitrogen, argon gas or combination
Conventional inert gas.
In the embodiment of the present invention, in step S13, the time for adding of mixed solution can be 0.5~6 hour, such as 0.5 small
When, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, it is 6 small
When etc.；Reaction time can be 0.5~24 hour, for example, 0.5 hour, 1 hour, 3 hours, 5 hours, 6 hours, 9 hours, it is 12 small
When, 15 hours, 18 hours, 20 hours, 24 hours etc..
Further, in preparation method provided in an embodiment of the present invention, during preparing fluoropolymer, in step
Before S11, can with the following steps are included:
Successively fluorochemical monomer shown in formula (III) is washed using akaline liquid and water, using molecular sieve to washing
Fluorochemical monomer afterwards is dried, and is filtered to the fluorochemical monomer after drying.
Wherein, akaline liquid can have the liquid of alkalinity for itself, be also possible to the aqueous solution of alkaline matter.Alkali
The aqueous solution of property substance includes but is not limited to: triethylamine aqueous solution, sodium bicarbonate aqueous solution, sodium hydrate aqueous solution, hydroxide
Aqueous solutions of potassium, aqueous sodium carbonate, wet chemical etc..Fluorochemical monomer is washed using the aqueous solution of alkaline matter
When, the mass fraction of fluorochemical monomer can be 200 parts~1000 parts, such as 200 parts, 300 parts, 400 parts, 500 parts, 600 parts,
700 parts, 800 parts, 900 parts, 1000 parts etc.；The mass fraction of alkaline matter can be 1 part~5 parts, such as 1 part, 2 parts, 3 parts, 4
Part, 5 parts etc.；The mass fraction of water can be 100 parts~500 parts, such as 100 parts, 200 parts, 300 parts, 400 parts, 500 parts.
It can use filter bag to be filtered the fluorochemical monomer after drying, the aperture of filter bag can be 0.45 μm.
It is understood that in step s 13, what is obtained at the end of reaction is the mixing of fluoropolymer and fluoride solvent
Solution can directly be diluted the mixed solution with fluoride solvent, to obtain the three-proofing coating of expected concentration；It can also pass through
Separating-purifying obtains solid flouropolymer, then fluoropolymer and fluoride solvent are mixed to get three-proofing coating.It is finally obtaining
Three-proofing coating in, fluoropolymer-containing mass fraction can be 1 part~10 parts, and the mass fraction of fluoride solvent is 30 parts~100
Part.
When being mixed the fluoropolymer of solid with fluoride solvent, mixing temperature can be 0 DEG C~25 DEG C, such as
0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C etc., incorporation time can be 1 hour~2 hours, such as 1 hour, 1.5 hours, 2
Hour etc., mechanical stirring can be used and mixed.
It is described further below by technical solution of the specific experiment data to the embodiment of the present invention.
Fluoride solvent used in following embodiment are as follows:
HFE-7100, the content of nona-fluoro butyl group methyl ether are 99.5%, are purchased from Minnesota Mining and Manufacturing Company；
HFE-7200, the content of nona-fluoro butyl group ether are 99.5%, are purchased from Minnesota Mining and Manufacturing Company；
Fluorocarbon solvent, specially perfluoro-cyclicether, including 75% perfluor (2- normal-butyl tetrahydrofuran) and 25% it is complete
Fluorine heptane is purchased from Shanghai Te Pu electron rich Science and Technology Ltd..
Embodiment 1
The present embodiment provides a kind of three-proofing coating, which includes fluoropolymer and fluoride solvent.Wherein, fluoropolymer
Object is to prepare using 2- (perfluoro capryl) ethylmethyl acrylate and methyl methacrylate as monomer through Raolical polymerizable
It obtains.
Specific preparation process is as follows:
Step 101,1g triethylamine and 100g pure water are configured to aqueous slkali, later by aqueous slkali and 200g fluorochemical monomer 2-
(perfluoro capryl) ethylmethyl acrylate is mixed and stirred for 2 hours, later moves into the mixed liquor of aqueous slkali and fluorochemical monomer
30 minutes are stood in separatory funnel, alkali cleaning is carried out to fluorochemical monomer；
Lower liquid in separatory funnel is mixed 30 minutes with 100g pure water, stands 30 minutes progress water again later
It washes, repeats the above water washing operations three times and be to upper and lower level liquid in separatory funnel colourless, each liquid separation takes lower liquid；
Fluorochemical monomer after washing is taken out from separatory funnel, the molecular sieve of 5g is added, it is 12 hours dry, hole is used later
Diameter is that 0.45 μm of filter bag is filtered the fluorochemical monomer after drying, the fluorochemical monomer that obtains that treated.
It step 102, will treated fluorochemical monomer 100g, methyl methacrylate 20g, 112g fluoride solvent HFE-7100
And the BPO (benzoyl peroxide) of 0.8g is uniformly mixed, and is completely dissolved BPO, obtains raw material mixed liquor.
Step 103,112g fluoride solvent HFE-7100 is added to have and is used as bottoming object in churned mechanically four-hole boiling flask,
Cooling device equipped with freezing liquid is connect with four-hole boiling flask, and it is -5 DEG C that cooling temperature, which is arranged,；Four-hole boiling flask is placed in oil bath
In heating device, and oil bath heating device is made to be warming up to 85 DEG C, after temperature is stablized, under nitrogen protection, step 102 is obtained
Raw material mixed liquor be at the uniform velocity added drop-wise in four-hole boiling flask under the action of peristaltic pump, be added dropwise in 2 hours；Later after continuation of insurance
Temperature is reacted after 3 hours to be terminated, and fluoropolymer solutions are obtained.
Step 104, the mass concentration for the fluoropolymer solutions that step 103 obtains is diluted to 5% using HFE-7100,
Obtain the three-proofing coating of the present embodiment.
The three-proofing coating appearance colorless of the present embodiment is transparent.
It will be dipped in the three-proofing coating having a size of 3cm × 3cm, the copper-clad plate through ethanol washing and drying, and take out set immediately
It is dried up in ventilation, forms fluoro-containing copolymer film on copper-clad plate surface and obtain test sample.It is formed by fluoropolymer-containing
Film is colorless and transparent.With the SL200K type (similarly hereinafter) of Ke Nuo Industrial Co., Ltd, the U.S. it is dynamic/Static water contact angle tester is to covering
The water contact angle of the fluoro-containing copolymer film on copper sheet surface is tested, and result is 110.4 °；GB6458-86 according to national standards
In requirement, after test sample is placed 48 hours in HL-60-33 type salt spray tester, test sample surface is without change
Change, repetition measurement water contact angle is 110.24 °.
Embodiment 2
The present embodiment provides a kind of three-proofing coating, which includes fluoropolymer and fluoride solvent.Wherein, fluoropolymer
Object is to be prepared using 2- (perfluoro capryl) ethyl propylene acid esters and methyl methacrylate as monomer through Raolical polymerizable.
Specific preparation process is as follows:
Step 201,5g sodium bicarbonate solid and 500g pure water are configured to aqueous slkali, it is later that aqueous slkali is fluorine-containing with 500g
Monomer 2- (perfluoro capryl) ethyl propylene acid esters is mixed and stirred for 2 hours, later moves the mixed liquor of aqueous slkali and fluorochemical monomer
Enter in separatory funnel and stand 30 minutes, alkali cleaning is carried out to fluorochemical monomer；
Lower liquid in separatory funnel is mixed 30 minutes with 500g pure water, stands 30 minutes progress water again later
It washes, repeats the above water washing operations three times and be to upper and lower level liquid in separatory funnel colourless, each liquid separation takes lower liquid；
Fluorochemical monomer after washing is taken out from separatory funnel, the molecular sieve of 25g is added, 12 hours dry, Zhi Houyong
Aperture is that 0.45 μm of filter bag is filtered the fluorochemical monomer after drying, the fluorochemical monomer that obtains that treated.
It step 202, will treated fluorochemical monomer 500g, methyl methacrylate 40g, 756g fluoride solvent HFE-7100
And the AIBN (azodiisobutyronitrile) of 4g is uniformly mixed, and is completely dissolved AIBN, obtains raw material mixed liquor.
Step 203,504g fluoride solvent HFE-7100 is added to have and is used as bottoming object in churned mechanically four-hole boiling flask,
Cooling device equipped with freezing liquid is connect with four-hole boiling flask, and it is -5 DEG C that cooling temperature, which is arranged,；Four-hole boiling flask is placed in oil bath
In heating device, and oil bath heating device is made to be warming up to 85 DEG C, after temperature is stablized, under nitrogen protection, step 202 is obtained
Raw material mixed liquor be at the uniform velocity added drop-wise in four-hole boiling flask under the action of peristaltic pump, be added dropwise in 3 hours；Later after continuation of insurance
Temperature is reacted after 3 hours to be terminated, and fluoropolymer solutions are obtained.
Step 204, the mass concentration for the fluoropolymer solutions that step 203 obtains is diluted to using fluorocarbon solvent
10%, obtain the three-proofing coating of the present embodiment.
Three-proofing coating appearance colorless provided in this embodiment is transparent.
It will be dipped in the three-proofing coating having a size of 3cm × 3cm, the copper-clad plate through ethanol washing and drying, and take out set immediately
It is dried up in ventilation, forms fluoro-containing copolymer film on copper-clad plate surface and obtain test sample.It is formed by fluoropolymer-containing
Film is colorless and transparent.With dynamic/Static water contact angle tester to the water contact angle of the fluoro-containing copolymer film on copper-clad plate surface into
Row test, result are 113.4 °；Test sample is put in HL-60-33 type salt spray tester according to the condition of embodiment 1
After setting 96 hours, test sample surface is unchanged, and repetition measurement water contact angle is 113.36 °.
Embodiment 3
The present embodiment provides a kind of three-proofing coating, which includes fluoropolymer and fluoride solvent.Wherein, fluoropolymer
Object is to be prepared using 2- (perfluoro capryl) ethyl propylene acid esters and methyl methacrylate as monomer through Raolical polymerizable.
Specific preparation process is as follows:
Step 301,2.5g sodium hydrate solid and 200g pure water are configured to aqueous slkali, later contain aqueous slkali and 400g
Fluorine monomer 2- (perfluoro capryl) ethyl propylene acid esters is mixed and stirred for 2 hours, later by the mixed liquor of aqueous slkali and fluorochemical monomer
It moves into separatory funnel and stands 30 minutes, alkali cleaning is carried out to fluorochemical monomer；
Lower liquid in separatory funnel is mixed 30 minutes with 200g pure water, stands 30 minutes progress water again later
It washes, repeats the above water washing operations three times and be to upper and lower level liquid in separatory funnel colourless, each liquid separation takes lower liquid；
Fluorochemical monomer after washing is taken out from separatory funnel, the molecular sieve of 20g is added, 12 hours dry, Zhi Houyong
Aperture is that 0.45 μm of filter bag is filtered the fluorochemical monomer after drying, the fluorochemical monomer that obtains that treated.
It step 302, will treated fluorochemical monomer 400g, methyl methacrylate 8g, 979g fluoride solvent HFE-7200
And the AIBN of 2.4g is uniformly mixed, and is completely dissolved AIBN, obtains raw material mixed liquor.
Step 303,652g fluoride solvent HFE-7200 is added to have and is used as bottoming object in churned mechanically four-hole boiling flask,
Cooling device equipped with freezing liquid is connect with four-hole boiling flask, and it is -5 DEG C that cooling temperature, which is arranged,；Four-hole boiling flask is placed in oil bath
In heating device, and oil bath heating device is made to be warming up to 85 DEG C, after temperature is stablized, under nitrogen protection, step 302 is obtained
Raw material mixed liquor be at the uniform velocity added drop-wise in four-hole boiling flask under the action of peristaltic pump, be added dropwise in 4 hours；Later after continuation of insurance
Temperature is reacted after 2 hours to be terminated, and fluoropolymer solutions are obtained.
Step 304, the mass concentration using the fluoride solvent HFE-7200 fluoropolymer solutions for obtaining step 303 is dilute
It is interpreted as 1%, obtains the three-proofing coating of the present embodiment.
Three-proofing coating appearance colorless provided in this embodiment is transparent.
It will be dipped in the three-proofing coating having a size of 3cm × 3cm, the copper-clad plate through ethanol washing and drying, and take out set immediately
It is dried up in ventilation, forms fluoro-containing copolymer film on copper-clad plate surface and obtain test sample.It is formed by fluoropolymer-containing
Film is colorless and transparent.With dynamic/Static water contact angle tester to the water contact angle of the fluoro-containing copolymer film on copper-clad plate surface into
Row test, result are 114.73 °；By test sample according to the condition of embodiment 1 in HL-60-33 type salt spray tester
After placing 120 hours, test sample surface is unchanged, and repetition measurement water contact angle is 113.34 °.
Embodiment 4
The present embodiment provides a kind of three-proofing coating, which includes fluoropolymer and fluoride solvent.Wherein, fluoropolymer
Object is to prepare using 2- (perfluoro hexyl) ethylmethyl acrylate and methyl methacrylate as monomer through Raolical polymerizable
It obtains.
Specific preparation process is as follows:
Step 401,2g potassium hydroxide solid and 100g pure water are configured to aqueous slkali, it is later that aqueous slkali is fluorine-containing with 200g
Monomer 2- (perfluoro hexyl) ethylmethyl acrylate is mixed and stirred for 2 hours, and the mixed liquor of aqueous slkali and fluorochemical monomer moves into
30 minutes are stood in separatory funnel, alkali cleaning is carried out to fluorochemical monomer；
Lower liquid in separatory funnel is mixed 30 minutes with 100g pure water, stands 30 minutes progress water again later
It washes, repeats the above water washing operations three times and be to upper and lower level liquid in separatory funnel colourless, each liquid separation takes lower liquid；
Fluorochemical monomer after washing is taken out from separatory funnel, the molecular sieve of 10g is added, 12 hours dry, Zhi Houyong
Aperture is that 0.45 μm of filter bag is filtered the fluorochemical monomer after drying, the fluorochemical monomer that obtains that treated.
It step 402, will treated fluorochemical monomer 200g, methyl methacrylate 20g, 528g fluoride solvent HFE-7100
And the AIBN of 1.32g is uniformly mixed, and is completely dissolved AIBN, obtains raw material mixed liquor.
Step 403,352g fluoride solvent HFE-7200 is added to have and is used as bottoming object in churned mechanically four-hole boiling flask,
Cooling device equipped with freezing liquid is connect with four-hole boiling flask, and it is -5 DEG C that cooling temperature, which is arranged,；Four-hole boiling flask is placed in oil bath
In heating device, and oil bath heating device is made to be warming up to 80 DEG C, after temperature is stablized, under nitrogen protection, step 402 is obtained
Raw material mixed liquor be at the uniform velocity added drop-wise in four-hole boiling flask under the action of peristaltic pump, be added dropwise in 2.5 hours；Continue later
Heat preservation is reacted after 2 hours to be terminated, and fluoropolymer solutions are obtained.
Step 404, the mass concentration using the fluoride solvent HFE-7100 fluoropolymer solutions for obtaining step 403 is dilute
It is interpreted as 5%, obtains the three-proofing coating of the present embodiment.
Three-proofing coating appearance colorless provided in this embodiment is transparent.
It will be dipped in the three-proofing coating having a size of 3cm × 3cm, the copper-clad plate through acetone washing and drying, and take out set immediately
It is dried up in ventilation, forms fluoro-containing copolymer film on copper-clad plate surface and obtain test sample.It is formed by fluoropolymer-containing
Film is colorless and transparent.With dynamic/Static water contact angle tester to the water contact angle of the fluoro-containing copolymer film on copper-clad plate surface into
Row test, result are 112.54 °；By test sample according to the condition of embodiment 1 in HL-60-33 type salt spray tester
After placing 96 hours, test sample surface is unchanged, and repetition measurement water contact angle is 112.24 °.
Embodiment 5
The present embodiment provides a kind of three-proofing coating, which includes fluoropolymer and fluoride solvent.Wherein, fluoropolymer
Object is to prepare using 2- (perfluoro hexyl) ethylmethyl acrylate and methyl methacrylate as monomer through Raolical polymerizable
It obtains.
Specific preparation process is as follows:
Step 501,2g sodium carbonate solid and 100g pure water are configured to aqueous slkali, later by aqueous slkali and the fluorine-containing list of 200g
Body 2- (perfluoro hexyl) ethylmethyl acrylate is mixed 2 hours, later moves the mixed liquor of aqueous slkali and fluorochemical monomer
Enter in separatory funnel and stand 30 minutes, alkali cleaning is carried out to fluorochemical monomer；
Lower liquid in separatory funnel is mixed 30 minutes with 100g pure water, stands 30 minutes progress water again later
It washes, repeats the above water washing operations three times and be to upper and lower level liquid in separatory funnel colourless, each liquid separation takes lower liquid；
Fluorochemical monomer after washing is taken out from separatory funnel, the molecular sieve of 10g is added, 12 hours dry, Zhi Houyong
Aperture is that 0.45 μm of filter bag is filtered the fluorochemical monomer after drying, the fluorochemical monomer that obtains that treated.
It step 502, will treated fluorochemical monomer 200g, methyl methacrylate 25g, 787g fluoride solvent HFE-7100
And the AIBN of 1.57g is uniformly mixed, and is completely dissolved AIBN, obtains raw material mixed liquor.
Step 503,525g fluoride solvent HFE-7200 is added to have and is used as bottoming object in churned mechanically four-hole boiling flask,
Cooling device equipped with freezing liquid is connect with four-hole boiling flask, and it is -5 DEG C that cooling temperature, which is arranged,；Four-hole boiling flask is placed in oil bath
In heating device, and oil bath heating device is made to be warming up to 80 DEG C, after temperature is stablized, under nitrogen protection, step 502 is obtained
Raw material mixed liquor be at the uniform velocity added drop-wise in four-hole boiling flask under the action of peristaltic pump, be added dropwise in 2.5 hours；Continue later
Heat preservation is reacted after 2 hours to be terminated, and fluoropolymer solutions are obtained.
Step 504, the mass concentration using the fluoride solvent HFE-7200 fluoropolymer solutions for obtaining step 503 is dilute
It is interpreted as 5%, obtains the three-proofing coating of the present embodiment.
Three-proofing coating appearance colorless provided in this embodiment is transparent.
It will be dipped in the sample solution having a size of 3cm × 3cm, the copper-clad plate through acetone washing and drying, and take out immediately
It is placed in ventilation drying, fluoro-containing copolymer film is formed on copper-clad plate surface and obtains test sample.It is formed by fluoropolymer
Film it is colorless and transparent.With dynamic/Static water contact angle tester to the water contact angle of the fluoro-containing copolymer film on copper-clad plate surface
It is tested, result is 111.39 °；By test sample according to the item of embodiment 1 in HL-60-33 type salt spray tester
After part is placed 96 hours, test sample surface is unchanged, and repetition measurement water contact angle is 111.76 °.
Embodiment 6
The present embodiment provides a kind of three-proofing coating, which includes fluoropolymer and fluoride solvent.Wherein, fluoropolymer
Object is to prepare using 2- (perfluoro hexyl) ethylmethyl acrylate and methyl methacrylate as monomer through Raolical polymerizable
It obtains.
Specific preparation process is as follows:
Step 601,2g sodium bicarbonate solid and 100g pure water are configured to aqueous slkali, it is later that aqueous slkali is fluorine-containing with 200g
Monomer 2- (perfluoro hexyl) ethylmethyl acrylate is mixed and stirred for 2 hours, later by the mixing of aqueous slkali and fluorochemical monomer
Liquid moves into separatory funnel and stands 30 minutes, carries out alkali cleaning to fluorochemical monomer；
Lower liquid in separatory funnel is mixed 30 minutes with 100g pure water, stands 30 minutes progress water again later
It washes, repeats the above water washing operations three times and be to upper and lower level liquid in separatory funnel colourless, each liquid separation takes lower liquid；
Fluorochemical monomer after washing is taken out from separatory funnel, the molecular sieve of 10g is added, 12 hours dry, Zhi Houyong
Aperture is that 0.45 μm of filter bag is filtered the fluorochemical monomer after drying, the fluorochemical monomer that obtains that treated.
It step 602, will treated fluorochemical monomer 200g, methyl methacrylate 33g, 559g fluoride solvent HFE-7100
And the AIBN of 1.39g is uniformly mixed, and is completely dissolved AIBN, obtains raw material mixed liquor.
Step 603,372g fluoride solvent HFE-7200 is added to have and is used as bottoming object in churned mechanically four-hole boiling flask,
Cooling device equipped with freezing liquid is connect with four-hole boiling flask, and it is -5 DEG C that cooling temperature, which is arranged,；Four-hole boiling flask is placed in oil bath
In heating device, and oil bath heating device is made to be warming up to 80 DEG C, after temperature is stablized, under nitrogen protection, step 102 is obtained
Raw material mixed liquor be at the uniform velocity added drop-wise in four-hole boiling flask under the action of peristaltic pump, be added dropwise in 2.5 hours；Continue later
Heat preservation is reacted after 2 hours to be terminated, and fluoropolymer solutions are obtained.
Step 604, the mass concentration using the fluoride solvent HFE-7200 fluoropolymer solutions for obtaining step 603 is dilute
It is interpreted as 2%, obtains the three-proofing coating of the present embodiment.
Three-proofing coating appearance colorless provided in this embodiment is transparent.
It will be dipped in the sample solution having a size of 3cm × 3cm, the copper-clad plate through ethanol washing and drying, and take out immediately
It is placed in ventilation drying, fluoro-containing copolymer film is formed on copper-clad plate surface and obtains test sample.It is surveyed with dynamic/Static water contact angles
Examination instrument tests the water contact angle of the fluoro-containing copolymer film on copper-clad plate surface, and result is 110.47 °；Test sample is existed
After placing 48 hours in HL-60-33 type salt spray tester according to the condition of embodiment 1, test sample surface is unchanged, multiple
Surveying water contact angle is 110.74 °.
Comparative example 1
This comparative example the difference from embodiment 1 is that, with octadecyl methacrylate substitute 2- (perfluoro capryl) ethyl third
Olefin(e) acid ester.
The three-proofing coating appearance of this comparative example is in pale yellow transparent, coloration 80APHA.
It is in pale yellow transparent in the polymer thin film outward appearance that copper-clad plate surface is formed, water contact angle is 99.74 °.
Comparative example 2
The difference of this comparative example and embodiment 3 is, substitutes 2- (perfluoro capryl) ethyl with trifluoroethyl methacrylate
Acrylate.
The three-proofing coating appearance of this comparative example is in pale yellow transparent, coloration 100APHA.
It is in pale yellow transparent in the polymer thin film outward appearance that copper-clad plate surface is formed, water contact angle is 75.34 °.
Comparative example 3
The difference of this comparative example and embodiment 4 is, substitutes 2- (perfluoro hexyl) ethyl with Hexafluorobutyl mathacrylate
Methacrylate.
The three-proofing coating appearance of this comparative example is in pale yellow transparent, coloration 80APHA.
It is in pale yellow transparent in the polymer thin film outward appearance that copper-clad plate surface is formed, water contact angle is 82.35 °.
Comparative example 4
The difference of this comparative example and embodiment 6 is, substitutes 2- (perfluoro hexyl) second with methacrylic acid hexafluoro isopropyl ester
Methyl acrylate.
The three-proofing coating appearance of this comparative example is in pale yellow transparent, coloration 100APHA.
It is in pale yellow transparent in the polymer thin film outward appearance that copper-clad plate surface is formed, water contact angle is 70.09 °.
The product main performance of the above various embodiments and comparative example is summarized as follows shown in table:
| Appearance | Water contact angle (°) | |
| Embodiment 1 | It is colorless and transparent | 110.4 |
| Embodiment 2 | It is colorless and transparent | 113.4 |
| Embodiment 3 | It is colorless and transparent | 114.73 |
| Embodiment 4 | It is colorless and transparent | 112.54 |
| Embodiment 5 | It is colorless and transparent | 111.39 |
| Embodiment 6 | It is colorless and transparent | 110.47 |
| Comparative example 1 | Pale yellow transparent, coloration 80APHA | 99.74 |
| Comparative example 2 | Pale yellow transparent, coloration 100APHA | 75.34 |
| Comparative example 3 | Pale yellow transparent, coloration 80APHA | 82.35 |
| Comparative example 4 | Pale yellow transparent, coloration 100APHA | 70.09 |
It is formed by above data as can be seen that three-proofing coating provided in an embodiment of the present invention is after matrix surface film forming
Polymer film is colorless and transparent, and initial water contact angle can reach 110 ° or more, after being placed 48 hours or more under the conditions of salt fog,
Water contact angle does not change substantially, it is seen that three-proofing coating provided in an embodiment of the present invention has good waterproof performance, grease proofness
Energy and anti-pollution, meet the needs of 3C wiring board and electronic component are for three-proofing coating.Also, the embodiment of the present invention provides
Three-proofing coating in addition to fluoropolymer and fluoride solvent, be free of other auxiliary agents, and without baking, ultraviolet light solidification can form a film,
Use process is simple, at low cost.
The above is merely for convenience of it will be understood by those skilled in the art that technical solution of the present invention, not to limit
The present invention.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this
Within the protection scope of invention.
Claims (10)
1. a kind of three-proofing coating, which is characterized in that the three-proofing coating includes fluoropolymer and fluoride solvent；
The fluoropolymer has structural unit shown in formula (I) and formula (II):
Wherein, X be hydrogen atom, alkyl or halogen atom with 1~3 carbon atom,
Y is the aliphatic group with 1~3 carbon atom,
Rf is the perfluoroalkyl with 4~10 carbon atoms；
Wherein, A1For hydrogen atom, methyl or the halogen atom in addition to fluorine atom,
A2For the alkyl with 1~10 carbon atom.
2. three-proofing coating according to claim 1, which is characterized in that shown in structural unit shown in formula (I) and formula (II)
The quantitative proportion of structural unit are as follows: (1~10): 1.
3. three-proofing coating according to claim 1, which is characterized in that the fluoride solvent is selected from nona-fluoro butyl group ether, nine fluorine
At least one of butyl methyl ether, tetra- fluoro ethyl -2,2,2- trifluoroethyl ether of 1,1,2,2- and fluorocarbon solvent.
4. described in any item three-proofing coatings according to claim 1~3, which is characterized in that in the three-proofing coating, the fluoropolymer
The mass fraction of object is 1 part~10 parts, and the mass fraction of the fluoride solvent is 30 parts~100 parts.
5. a kind of preparation method of three-proofing coating, which is characterized in that the preparation method includes:
Step S1 makes acrylate monomer shown in fluorochemical monomer and formula shown in formula (III) (IV) carry out free radical polymerization anti-
It should obtain fluoropolymer；
Wherein, X be hydrogen atom, alkyl or halogen atom with 1~3 carbon atom,
Y is the aliphatic group with 1~3 carbon atom,
Rf is the perfluoroalkyl with 4~10 carbon atoms；
Wherein, A1For hydrogen atom, methyl or the halogen atom in addition to fluorine atom,
A2For the alkyl with 1~10 carbon atom；
The fluoropolymer and fluoride solvent are mixed to get the three-proofing coating by step S2.
6. preparation method according to claim 5, which is characterized in that step S1 includes:
Step S11 by acrylate monomer shown in fluorochemical monomer shown in formula (III), formula (IV), initiator and described contains
Fluorous solvent is uniformly mixed and obtains mixed solution；
The fluoride solvent is added into reaction vessel and is warming up to preset temperature under inert gas protection by step S12；
The mixed solution is added dropwise in the reaction vessel by step S13, and reaction preset time obtains described after being added dropwise
Fluoropolymer.
7. preparation method according to claim 6, which is characterized in that the mass fraction of fluorochemical monomer shown in formula (III)
It is 200 parts~1000 parts, the mass fraction of acrylate monomer shown in formula (IV) is 10 parts~40 parts, the matter of the initiator
Measuring number is 0.4 part~4 parts, the fluoride solvent in fluoride solvent and the reaction vessel in the mixed solution it is total
Mass fraction is 500 parts~5000 parts.
8. preparation method according to claim 6, which is characterized in that the fluoride solvent is selected from nona-fluoro butyl group ether, nine
Fluorine butyl methyl ether, 1,1,2,2- tetra- fluoro ethyl -2,2, at least one of 2- trifluoroethyl ether and fluorocarbon solvent are described default
Temperature is 50 DEG C~100 DEG C.
9. preparation method according to claim 6, which is characterized in that before step S11, the preparation method is also wrapped
It includes:
Successively fluorochemical monomer shown in formula (III) is washed using akaline liquid and water, using molecular sieve to washing after
Fluorochemical monomer is dried, and is filtered to the fluorochemical monomer after drying.
10. preparation method according to claim 5, which is characterized in that in step S2, the fluoropolymer-containing mass parts
Number is 1 part~10 parts, and the mass fraction of the fluoride solvent is 30 parts~100 parts；
Mixing temperature is 0 DEG C~25 DEG C, and incorporation time is 1 hour~2 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669387A (en) * | 2019-10-29 | 2020-01-10 | 卓聪（上海）环保科技发展有限公司 | Insulating protective film coating and preparation method thereof |
| CN111218200A (en) * | 2020-01-17 | 2020-06-02 | 北京信为兢创科技有限公司 | High-wear-resistance moisture-proof coating composition and preparation method and application thereof |
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| JPH03134075A (en) * | 1983-03-29 | 1991-06-07 | Union Carbide Chem & Plast Co Inc | Ultraviolet-curable conformal coating material |
| CN104271690A (en) * | 2012-05-11 | 2015-01-07 | 大金工业株式会社 | Coating composition for water-proofing and moisture-proofing |
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2017
- 2017-12-08 CN CN201711296423.2A patent/CN109897493A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03134075A (en) * | 1983-03-29 | 1991-06-07 | Union Carbide Chem & Plast Co Inc | Ultraviolet-curable conformal coating material |
| CN104271690A (en) * | 2012-05-11 | 2015-01-07 | 大金工业株式会社 | Coating composition for water-proofing and moisture-proofing |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669387A (en) * | 2019-10-29 | 2020-01-10 | 卓聪（上海）环保科技发展有限公司 | Insulating protective film coating and preparation method thereof |
| CN111218200A (en) * | 2020-01-17 | 2020-06-02 | 北京信为兢创科技有限公司 | High-wear-resistance moisture-proof coating composition and preparation method and application thereof |
| CN111218200B (en) * | 2020-01-17 | 2022-03-01 | 北京信为兢创科技有限公司 | High-wear-resistance moisture-proof coating composition and preparation method and application thereof |
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