CN110922526A - Fluorine-containing polymer and protective coating agent containing same - Google Patents
Fluorine-containing polymer and protective coating agent containing same Download PDFInfo
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- CN110922526A CN110922526A CN201911177507.3A CN201911177507A CN110922526A CN 110922526 A CN110922526 A CN 110922526A CN 201911177507 A CN201911177507 A CN 201911177507A CN 110922526 A CN110922526 A CN 110922526A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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 provides a fluorine-containing polymer and a protective coating agent containing the fluorine-containing polymer. The polymerized monomers of the fluoropolymer include: perfluoroalkyl acrylate monomer, trifunctional acrylate monomer containing siloxane structure, alkyl acrylate monomer and acrylate monomer containing aliphatic ring or aromatic ring. The fluorine-containing polymer has a dendritic space network structure, the amido bonds in the molecules can generate hydrogen bond interaction, and a benzene ring or an aliphatic ring structure is introduced, so that a unique protective layer with the amido bonds and rigid benzene rings or aliphatic rings is formed on the surface of a polymer film. The protective coating agent containing the fluorine-containing polymer has strong adhesive force, high hardness, excellent water and oil resistance and excellent acid and alkali resistance.
Description
Technical Field
The invention relates to a fluorine-containing polymer and a protective coating agent containing the fluorine-containing polymer, in particular to a protective coating agent applied to electronic components.
Background
With the spread of multifunctional smart electronic products represented by smart phones and tablet computers, components and printed circuit boards of these smart electronic products have few extra gaps because a large number of electronic components are arranged inside a small housing, and thus it is difficult to package the products with silicone rubber that has been used conventionally. The thickness of the non-fluorine waterproof and moisture-proof coating film is more than 100 μm to achieve the expected effect; fluoroacrylate copolymers are preferred for thin (less than 1 μm) coatings on the surface of loop substrates. Since the smart electronic product is corroded by acid, alkali or salt generated in rain or moisture, fog, sweat, etc., and a short circuit of a circuit is damaged, the protective coating agent is required to have strict acid-base resistance and salt-fog resistance. However, the fluorine-containing waterproof and moisture-proof coating agent of the existing electronic product has the problems of poor adhesion, hardness, acid and alkali resistance and the like, so that the protection effect is poor, and the effect is reduced along with the time, so that the problems of misoperation and poor contact of the electronic product occur.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the protective coating agent with good adhesive force, high hardness, strong acid and alkali resistance and excellent water and oil resistance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the present invention provides a fluoropolymer whose polymerized monomers include: perfluoroalkyl acrylate monomer, trifunctional acrylate monomer containing siloxane structure, alkyl acrylate monomer and acrylate monomer containing aliphatic ring or aromatic ring.
The amide bond in the trifunctional acrylate monomer containing the siloxane structure can improve the adhesive force and the hardness of the polymer film, due to the existence of the trifunctional degree, the monomer can form a dendritic high-molecular polymer through polymerization, meanwhile, hydrogen bond interaction can be generated among amide bonds, the aliphatic ring or benzene ring structure in the acrylate monomer containing the aliphatic ring or aromatic ring has rigidity, and the amide bonds and the benzene ring or the aliphatic ring form a unique protective layer on the surface of the polymer film, so that the acid-base resistance and the salt spray resistance of the product can be effectively improved.
Further, the perfluoroalkyl acrylate monomer used in the present invention has the following structural formula:
wherein X is a fluorine atom, a chlorine atom, a hydrogen atom or a methyl group;
y is C1-10 aliphatic group, C6-10 aromatic group, C6-10 cyclic aliphatic group, -CH2CH2N(R1)SO2or-CH2CH(OY1)CH2Wherein R1 is an alkyl group having a carbon number of 1 to 4, and Y1 is a hydrogen atom or an acetyl group;
rf is a linear fluoroalkyl group having 1 to 6 carbon atoms.
Specific examples of the above perfluoroalkyl acrylate monomers are as follows:
the perfluoroalkyl acrylate monomers mentioned above may be used alone or in combination.
The perfluoroalkyl acrylate monomer can improve the water and oil resistance of the protective coating agent, and the perfluoroalkyl acrylate monomer is preferably CH from the aspects of cost and environmental protection2＝C(CH3)COOCH2CH2C4F9。
The trifunctional acrylate monomer having a siloxane structure used in the present invention has the following structural formula:
wherein R is alkoxy with carbon number of 1-4, fluorine atom, bromine atom, chlorine atom or iodine atom.
In some embodiments, R is-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)CH3Or a chlorine atom.
In some embodiments, R is-OCH2CH3、-OCH2CH2CH3or-OCH (CH)3)CH3. The electron-donating effect of the substituent is stronger, and the reactivity can be increased.
The alkyl acrylate monomer used in the present invention is alkyl acrylate having 10 to 30 carbon atoms or alkyl methacrylate having 10 to 30 carbon atoms. The longer the alkyl chain, the better the waterproofness, the higher the softening point temperature, the better the flexibility and the stronger the plasticity of the film.
The alkyl acrylate monomer is selected from one or more of behenyl acrylate, behenyl methacrylate, stearyl acrylate, stearyl methacrylate, lauryl acrylate and lauryl methacrylate, and stearyl acrylate is preferred.
The acrylate monomer containing an aliphatic ring or an aromatic ring used in the present invention is selected from one or more of isobornyl methacrylate, benzyl methacrylate and cyclohexyl methacrylate, and benzyl methacrylate is preferred. The hard monomer containing the alicyclic ring or aromatic ring monomer attribute can improve rigidity, glass transition temperature, mechanical property and chemical corrosion resistance, simultaneously has good thermal stability, and enhances toughness and impact strength of the polymer.
In some embodiments, the perfluoroalkyl acrylate monomer comprises 75 to 90% of the total mass of polymerized monomers of the fluoropolymer, for example: 75%, 78%, 80%, 85%, 90%.
In some embodiments, the trifunctional acrylate monomer containing a siloxane structure comprises 1-3% of the total mass of polymerized monomers of the fluoropolymer, for example: 1%, 1.5%, 2%, 2.5%, 3%.
In some embodiments, the alkyl acrylate monomer comprises 5 to 20% of the total mass of polymerized monomers of the fluoropolymer.
In other embodiments, the alkyl acrylate monomer comprises 5 to 10% of the total mass of polymerized monomers of the fluoropolymer, for example: 5%, 6%, 7%, 8%, 9%, 10%.
In other embodiments, the alkyl acrylate monomer comprises 10 to 20% of the total mass of polymerized monomers of the fluoropolymer, for example: 10%, 15%, 19%, 20%.
In some embodiments, the aliphatic or aromatic ring containing acrylate monomer comprises 1 to 10% by weight of the total polymerized monomers of the fluoropolymer.
In other embodiments, the aliphatic or aromatic ring containing acrylate monomer comprises from 1 to 5% by weight of the total polymerized monomers of the fluoropolymer, for example: 1%, 2%, 3%, 4%, 5%.
In other embodiments, the aliphatic or aromatic ring containing acrylate monomer comprises from 8 to 10% by weight of the total polymerized monomers of the fluoropolymer, for example: 8%, 9% and 10%.
The perfluoroalkyl acrylate monomer used in the invention is used for improving the water and oil resistance of the polymer film, when the content of the perfluoroalkyl acrylate monomer is too low or the content of other monomers is too high, the water and oil resistance can be influenced, and when the content of other monomers is too low, the other properties of the film can be reduced, for example, when the content of the trifunctional acrylate monomer is too low, the adhesive force, the hardness and the like of the film can be reduced, when the content of the alkyl acrylate monomer is too low, the flexibility of the film can be influenced, and when the content of the acrylate monomer containing an aliphatic ring or an aromatic ring is too low, the thermal stability, the chemical.
The fluoropolymer of the present invention may be prepared by any of the usual polymerization methods, such as: solution polymerization, suspension polymerization, emulsion polymerization.
Further, the fluorine-containing polymer of the invention is prepared by a solution polymerization method, and specifically comprises the following steps:
(1) adding a perfluoroalkyl acrylate monomer, a trifunctional acrylate monomer with a siloxane structure, an alkyl acrylate monomer and an acrylate monomer containing an aliphatic ring or an aromatic ring into a four-neck flask, adding perfluorobutyl ether (HFE7200) as a reaction solvent, and adding a proper amount of an initiator;
(2) and (2) introducing nitrogen into the device in the step (1) for purging, raising the reaction temperature to 65-80 ℃, reacting for 4-8h, and obtaining the fluorine-containing polymer stock solution after the reaction is finished.
Further, the initiator is an oil-soluble initiator and is selected from one or more of azobisisobutyronitrile, azobisisopentonitrile, phthalide peroxide, di-tert-butyl peroxide, lauryl peroxide, tert-butyl peroxypivalate and diisopropyl peroxydicarbonate, and preferably an azo initiator.
In some embodiments, the fluoropolymer has a weight average molecular weight (Mw) of 30000-70000.
In other embodiments, the fluoropolymer has a weight average molecular weight (Mw) of 40000 and 60000.
The molecular weight of the fluorine-containing polymer is too small, which indicates that the reaction degree is not enough, the conversion rate is not high, and the film forming property of the polymer is not good; too high molecular weight of the fluoropolymer may cause implosion of the polymer and stacking of polymer molecules, which affects the performance of the film.
In another aspect, the present invention provides a protective coating agent comprising the above-described fluoropolymer. The protective coating agent can be used directly or after diluting the fluoropolymer stock solution.
In some embodiments, the protective coating agent is obtained by diluting the fluoropolymer with perfluorobutyl methyl ether (HFE7100) to 2% or 4%.
The protective coating agent provided by the invention is suitable for being used as a protective coating agent of electronic components.
Further, the electronic component is preferably a Printed Circuit Board (PCB).
The invention has the beneficial effects that:
on one hand, the three-functionality acrylic ester monomer structure containing the siloxane structure, which is used by the invention, contains a hydrolyzable group of a silane coupling agent and a polymerizable acrylic double bond, so that the free radical polymerization can be carried out, the cohesiveness with an inorganic base material can be improved through the siloxane structure contained in the molecule, the amide bond in the molecule has a remarkable effect on improving the flexibility of a polymer film, the adhesive force and the hardness of a protective coating are greatly improved, and meanwhile, three double bonds in the structure increase active sites and shorten the reaction time;
on the other hand, the monomer used in the invention forms the dendritic high molecular polymer through polymerization, the polymer has a spatial network structure, due to the unique branched molecular structure, the molecules are not entangled, the amido bonds in the molecules can generate hydrogen bond interaction, and in addition, the introduction of a rigid benzene ring or aliphatic ring structure enables the surface of the polymer film to form a unique protective layer containing amido bonds and benzene rings or aliphatic rings, thereby effectively preventing the invasion of corrosive substances such as acid, alkali and the like, improving the acid-base resistance and salt mist resistance of the product, and simultaneously, the existence of the fluorine-containing alkyl with low carbon chain improves the water resistance and oil resistance and is environment-friendly.
Definition of terms
All ranges cited herein are inclusive, unless expressly stated to the contrary.
The terms "a" or "an" are used herein to describe elements and components described herein. This is done merely for convenience and to provide a general sense of the scope of the invention. Such description should be understood to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise. "plural" means two or more.
The numbers in this disclosure are approximate, regardless of whether the word "about" or "approximately" is used. The numerical value of the number may have differences of 1%, 2%, 5%, 7%, 8%, 10%, etc. Whenever a number with a value of N is disclosed, any number with a value of N +/-1%, N +/-2%, N +/-3%, N +/-5%, N +/-7%, N +/-8% or N +/-10% is explicitly disclosed, wherein "+/-" means plus or minus, and a range between N-10% and N + 10% is also disclosed.
The following definitions, as used herein, should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of elements, and the 75 th version of the handbook of chemistry and Physics, 1994. In addition, general principles of Organic Chemistry can be found in the descriptions of "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and JerryMarch, John Wiley & Sons, New York:2007, the entire contents of which are incorporated herein by reference.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can also be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific section is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
Detailed Description
The preparation method of the trifunctional acrylate monomer with the siloxane structure refers to Chinese patent CN106279242A, wherein R group is-OCH2CH3The specific preparation process of the trifunctional acrylate monomer containing the siloxane structure comprises the following steps:
adding 35.79g of pentaerythritol triacrylate (PETA) and 0.06g of dibutyltin dilaurate into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, uniformly stirring, then dropwise adding 24.74g of gamma-Isocyanate Propyl Triethoxysilane (IPTS) through a constant-pressure dropping funnel, controlling the dropwise adding speed, keeping the reaction temperature at 50 ℃ until the gamma-isocyanate propyl triethoxysilane completely reacts, washing with petroleum ether for 2 times to obtain the compound with the R group of-OCH2CH3The trifunctional acrylate monomer having a siloxane structure of (a).
The following are only specific examples 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.
Example 1
Into a four-necked flask was charged 15g of perfluorobutyl ethyl methacrylate (CH)2＝C(CH3)COOCH2CH2C4F9) 1g of benzyl methacrylate, 3.8g of stearyl acrylate and 0.2g of a trifunctional acrylate monomer containing a siloxane structure (R is-OCH)2CH3) Adding 0.1g of azodiisovaleronitrile, adding 80g of hydrofluoroether perfluorobutyl ether as a reaction solvent, carrying out nitrogen purging for 1min, heating to 70 ℃, and reacting for 4h to obtain the fluorine-containing polymer stock solution.
The molecular weight of the fluoropolymer raw liquid was measured by GPC using a fluorine-based solvent [ HFE 7100/tetrahydrofuran 90/10 (by weight) ] as an eluent, and the weight average molecular weight was 42895.
Example 2
Into a four-necked flask was charged 16g of perfluorobutyl ethyl methacrylate (CH)2＝C(CH3)COOCH2CH2C4F9) 1.6g of benzyl methacrylate, 2g of stearyl acrylate and 0.4g of a trifunctional acrylate monomer containing a siloxane structure (R is-OCH)2CH3) Adding 0.1g of azodiisovaleronitrile, adding 80g of hydrofluoroether perfluorobutyl ethyl ether as a reaction solvent, carrying out nitrogen purging for 1min, heating to 70 ℃, and reacting for 4h to obtain the fluorine-containing polymer stock solution.
The molecular weight of the fluoropolymer raw liquid was measured by GPC using a fluorine-based solvent [ HFE 7100/tetrahydrofuran 90/10 (by weight) ] as an eluent, and the weight average molecular weight was 51822.
Example 3
Into a four-necked flask was charged 18g of perfluorobutyl ethyl methacrylate (CH)2＝C(CH3)COOCH2CH2C4F9) 0.6g of benzyl methacrylate, 1.2g of stearyl acrylate and 0.2g of trifunctional acrylate containing a siloxane structureAlkenoic acid ester monomer (R is-OCH)2CH3) Adding 0.1g of azodiisovaleronitrile, adding 80g of hydrofluoroether perfluorobutyl ethyl ether as a reaction solvent, carrying out nitrogen purging for 1min, heating to 70 ℃, and reacting for 4h to obtain the fluorine-containing polymer stock solution.
The molecular weight of the fluoropolymer raw liquid was measured by GPC using a fluorine-based solvent [ HFE 7100/tetrahydrofuran 90/10 (by weight) ] as an eluent, and the weight-average molecular weight was 56795.
Example 4
Into a four-necked flask was charged 16g of perfluorobutyl ethyl methacrylate (CH)2＝C(CH3)COOCH2CH2C4F9) 2g of benzyl methacrylate, 1.4g of stearyl acrylate and 0.6g of a trifunctional acrylate monomer containing a siloxane structure (R is-OCH)2CH3) Adding 0.1g of azodiisovaleronitrile, adding 80g of hydrofluoroether perfluorobutyl ethyl ether as a reaction solvent, carrying out nitrogen purging for 1min, heating to 70 ℃, and reacting for 4h to obtain the fluorine-containing polymer stock solution.
The molecular weight of the fluoropolymer raw liquid was measured by GPC using a fluorine-based solvent [ HFE 7100/tetrahydrofuran 90/10 (by weight) ] as an eluent, and the weight-average molecular weight was 58265.
Comparative example 1
Into a four-necked flask was charged 18g of perfluorobutyl ethyl methacrylate (CH)2＝C(CH3)COOCH2CH2C4F9) 0.6g of benzyl methacrylate and 1.2g of octadecyl acrylate, 0.1g of azobisisovaleronitrile and 80g of hydrofluoroether perfluorobutyl ethyl ether as a reaction solvent were added, nitrogen purging was performed for 1min, the mixture was heated to 70 ℃ and reacted for 4 hours to obtain a fluoropolymer stock solution.
The molecular weight of the fluoropolymer raw liquid was measured by GPC using a fluorine-based solvent [ HFE 7100/tetrahydrofuran 90/10 (by weight) ] as an eluent, and the weight-average molecular weight was 27522.
Comparative example 2
Into a four-necked flask was charged 18g of perfluorobutyl ethyl methacrylate (CH)2＝C(CH3)COOCH2CH2C4F9) And 1.2g of octadecyl acrylate and 0.2g of trifunctional acrylate monomer containing a siloxane structure, adding 0.1g of azodiisovaleronitrile, adding 80g of hydrofluoroether perfluorobutyl ethyl ether as a reaction solvent, carrying out nitrogen purging for 1min, heating to 70 ℃, and reacting for 4h to obtain the fluorine-containing polymer stock solution.
The molecular weight of the fluoropolymer liquid was measured by GPC using a fluorine-based solvent [ HFE 7100/tetrahydrofuran 90/10 (by weight) ] as an eluent, and the weight-average molecular weight was 32668.
Test data
1. Water and oil repellency
After the fluoropolymer original liquids in examples 1 to 4 and comparative examples 1 to 2 were cooled to room temperature and layered, they were diluted to 2% by mass using 900g of perfluorobutyl methyl ether to obtain each protective coating agent (2%).
And (3) evaluating the waterproof and oilproof performance of the copper foil part on the test piece by using a contact angle meter, ultrasonically cleaning the PCB in acetone for 30min, cleaning and drying the PCB by using perfluorobutyl methyl ether, soaking the PCB in the protective coating agents (2%), and airing the PCB at room temperature for 10min to obtain the test piece. For these test pieces, the static contact angle of water for a droplet capacity of 2. mu.L and the static contact angle of hexadecane for a droplet capacity of 2. mu.L were measured using JC2000D4 contact angle measuring instrument manufactured by the digital technologies company of morning in Shanghai, and the results are shown in Table 1.
TABLE 1 evaluation results of water and oil repellency
From the results in table 1, it is understood that the protective coating agents obtained in examples 1 to 4 exhibited a large static contact angle with water, and it can be confirmed that they had good water repellency. Particularly, the sample pieces treated with the protective coating agents obtained in examples 2 to 4 exhibited high static water repellency to water and hexadecane, and possessed very excellent water and oil repellency.
2. Salt spray resistance
After the fluoropolymer original liquids in examples 1 to 4 and comparative examples 1 to 2 were cooled to room temperature and layered, each protective coating agent (4%) was obtained by diluting the fluoropolymer original liquids to 4% by mass using 400g of perfluorobutyl methyl ether.
Chemical resistance was evaluated by the salt spray test (GB/T2423.17-2008):
angle of the test piece: saline (NaCl) concentration at 20 ± 5 ° with respect to the vertical axis: 5 plus or minus 1 percent (mass ratio), and the pH value is 6.5-7.2;
the saturated air temperature is 57 +/-1 ℃, and the temperature of a saline test box is 35 +/-1 ℃;
the experimental equipment adopts a TK-YW120PL salt spray test box;
a polished copper substrate having a size of 2.0X 20X 50mm was used as a substrate, and the substrate was immersed in each of the above protective coating agents (4%) for 1 time, and then taken out and dried at room temperature for 30 min. After salt spraying, the appearance after 72h of the continuous spray test was evaluated in four courses of O (no change, no corrosion), + + +, + (severe, no treatment). The evaluation results are shown in Table 2.
TABLE 2 evaluation results of salt spray resistance
From the results in Table 2, it is understood that the protective coating agents obtained in examples 1 to 4 of the present invention are superior to those of comparative examples 1 to 2 in salt spray resistance, and the protective coating agents obtained in examples 2 and 4 can form a coating film superior in chemical resistance.
3. Adhesion force
In the experiment, a cross-cut Method is adopted for testing the coating adhesion, the test standards of the cross-cut Method mainly include ASTM D3359Method D, ISO 2409 and GB, and the test standard of ISO 2409 is mainly adopted for the experiment.
Different paint films determine different cross-hatch distances, which are also affected by the softness or hardness of the substrate (see table 3).
TABLE 3 Cross-hatch spacing for different paint film thicknesses corresponding to the substrate
| 0 to 60 mu m | 1 mm apart | Hard base material |
| 0 to 60 mu m | 2 mm apart | Soft base material |
| 60-120 microns | 2 mm apart | Hard or soft substrates |
| 121-250 micron | 3 mm apart | Hard or soft substrates |
And (3) testing procedures:
measuring the thickness of the paint film to determine a proper cutting distance;
cutting the paint film into a cross grid at a stable pressure and proper intervals;
cleaning to remove surface impurities, and placing the middle of the adhesive tape in parallel with the scribing grid;
the tape was torn at an angle close to 60 °, the state of the cut part was checked with the tape kept as a reference, and ISO 2409 stipulates that grade 0 or grade 1 is acceptable.
The test results are listed in the classification table, table 4.
Table 4 adhesion test results grading table
The evaluation results are shown in Table 5.
4. Hardness of
The test method for the hardness of the experimental coating adopts a method B (manual method) in national standard GB/T6739-. Once each scratch, the pencil tip was reground and the scratch was repeated five times for pencils of the same hardness grade. The test material is a group of Chinese high grade drawing pencils, and the hardness of the pencil lead is classified into 13 grades according to the industrial standard. Gradually decreases from the hardest 6H to 5H, 4H, 3H, 2H, H, then to HB with moderate hardness, and then from B, 2B to the softest 6B.
In the five-pass scratching experiment, if two or more passes of the pencil are considered not to scratch the bottom plate or the bottom layer coating film of the sample plate, the same experiment is carried out by using the pencil with the previous hardness mark until the pencil with the coating film broken by two or more passes is found out, and the hardness mark of the pencil is recorded. The evaluation results are shown in Table 5.
TABLE 5 adhesion and hardness evaluation results
| Numbering | Hardness of | Adhesion force |
| Example 1 | H | 4 stage |
| Example 2 | 3H | Grade 5 |
| Example 3 | H | 4 stage |
| Example 4 | 3H | Grade 5 |
| Comparative example 1 | HB | Stage 2 |
| Comparative example 2 | 2H | Grade 3 |
As is clear from the results in Table 5, the protective coating agents obtained in comparative example 1 had poor hardness, the protective coating agents obtained in comparative examples 1 to 2 had poor adhesion, the protective coating agents obtained in examples 1 to 4 had excellent hardness and adhesion, and the protective coating agents obtained in examples 2 and 4 had the best hardness and adhesion.
5. Acid and alkali resistance
The acid and alkali resistance test method for the experiment adopts a B soaking method in national standard GB/T9274-1988, strong acid and strong base test solutions with pH values of 2 and 12 are prepared, sufficient strong acid and strong base test solutions are poured into appropriate transparent containers respectively, the treated copper sheet is placed into the container and is completely immersed in the test solutions, a cover is covered, the corrosion condition of the copper sheet is observed, and the corrosion starting time is recorded.
The evaluation results are shown in Table 6.
TABLE 6 evaluation results of acid and alkali resistance
As can be seen from the results in Table 6, the acid and alkali resistance of the protective coating agents obtained in examples 1 to 4 is obviously better than that of comparative examples 1 to 2 and blank copper sheets.
From the above test data, it can be seen that the protective coating agents obtained in examples 1 to 4 have not only water-and oil-repellency, but also excellent properties in salt spray resistance, adhesion, hardness, and acid and alkali resistance.
Claims (10)
1. A fluoropolymer characterized in that polymerized monomers of the fluoropolymer comprise: perfluoroalkyl acrylate monomer, trifunctional acrylate monomer containing siloxane structure, alkyl acrylate monomer and acrylate monomer containing aliphatic ring or aromatic ring.
2. A fluoropolymer according to claim 1 wherein said perfluoroalkyl acrylate monomer has the formula:
wherein X is a fluorine atom, a chlorine atom, a hydrogen atom or a methyl group;
y is C1-10 aliphatic group, C6-10 aromatic group, C6-10 cyclic aliphatic group, -CH2CH2N(R1)SO2or-CH2CH(OY1)CH2Wherein R1 is an alkyl group having a carbon number of 1 to 4, and Y1 is a hydrogen atom or an acetyl group;
rf is a linear fluoroalkyl group having 1 to 6 carbon atoms.
3. A fluoropolymer according to claim 2 wherein said perfluoroalkyl acrylate monomer is
One or more of (a).
4. The fluorine-containing polymer according to claim 1, wherein the structure of the trifunctional acrylate monomer having a siloxane structure is:
wherein R is alkoxy with carbon number of 1-4, fluorine atom, bromine atom, chlorine atom or iodine atom.
5. The fluorine-containing polymer according to claim 1, wherein the alkyl acrylate monomer is alkyl acrylate having a carbon number of 10 to 30 or alkyl methacrylate having a carbon number of 10 to 30.
6. A fluoropolymer according to claim 5 wherein said alkyl acrylate monomer is one or more of behenyl acrylate, behenyl methacrylate, stearyl acrylate, stearyl methacrylate, lauryl acrylate, lauryl methacrylate.
7. The fluorine-containing polymer according to claim 1, wherein the acrylate monomer containing an aliphatic ring or an aromatic ring is one or more selected from isobornyl methacrylate, benzyl methacrylate and cyclohexyl methacrylate.
8. A fluoropolymer according to claim 1 wherein optionally the perfluoroalkyl acrylate monomer comprises 75-90% of the total mass of polymerized monomers of the fluoropolymer;
optionally, the trifunctional acrylate monomer containing the siloxane structure accounts for 1-3% of the total mass of the polymerized monomers of the fluorine-containing polymer;
optionally, the alkyl acrylate monomer accounts for 5-20% of the total mass of the polymerized monomers of the fluoropolymer;
optionally, the acrylate monomer containing an aliphatic ring or an aromatic ring accounts for 1 to 10% of the total mass of the polymerized monomers of the fluoropolymer.
9. A fluoropolymer according to any of claims 1 to 8 wherein the weight average molecular weight of the fluoropolymer is 30000-70000.
10. A protective coating agent comprising the fluorine-containing polymer according to any one of claims 1 to 9.
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