CN104513585A - Super-hydrophobic paint composition and super-hydrophobic coating therewith - Google Patents
Super-hydrophobic paint composition and super-hydrophobic coating therewith Download PDFInfo
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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Abstract
The invention provides a double-component super-hydrophobic paint composition and a super-hydrophobic coating therewith. The super-hydrophobic paint composition consists of an A component and a B component, wherein the A component includes: an inorganic particle, of which the surface is provided with hydroxyl groups, amino groups, epoxy groups or a combination thereof as reactive groups, a hydrophobically-modified epoxy resin, and an epoxy resin toughening agent; and the B component includes a curing agent. The coating formed by the super-hydrophobic paint composition is excellent in a super-hydrophobic performance and is enhanced in mechanical performances.
Description
Technical field
The present invention relates to the super hydrophobic coating composition based on epoxy resin-matrix.More specifically, the coating composition that can form the super-hydrophobic coat with excellent ultra-hydrophobicity and good mechanical properties is related to.The present invention also relates to the super-hydrophobic coat formed by described super hydrophobic coating composition.
Background technology
Occurring in nature has special infiltrating organism surface, as lotus leaf, water skipper leg, butterfly's wing, the desert beetle back of the body etc. provide inspiration for we design the novel boundary material of preparation always, people are by the inspiration of these biologies, by constructing micron and nanometer composite structure and modifying low-surface energy substance, prepare a series of super hydrophobic surface with self_cleaning effect, namely the static contact angle of base material to water is greater than 150 ° and the roll angle surface that is less than 10 °, has and wide application prospect in fabric, building surface and the field such as glass for vehicle window, antenna.
In general, super hydrophobic surface can be prepared by two kinds of methods: one is at the coarse micro-enzyme electrode of hydrophobic material surface (low surface energy) upper structure; Another kind is the material to uneven surface being modified low surface energy.Although it is not the report built about super-hydrophobic coat is at present a lot, strength of coating, snappiness, good to mechanical propertys such as the sticking power of base material, limit the application of super-hydrophobic coat.Up to the present, domestic also do not possess the super-hydrophobic coat of good mechanical properties or the report of coating, therefore prepares the super hydrophobic coating with good mechanical properties significant.
Chinese invention patent publication number 102285199A discloses a kind of preparation method of fiber-reinforced epoxy resin-based composite material super-hydrophobic surface, the method is by fiber reinforced material, inorganic material powders, epoxy resin glue and solidifying agent are mixed to get coating resin system according to a certain ratio, by coating the first layer fiber reinforced material, intermediate layer resin system, second layer fiber reinforced material, repeatedly obtain composite material preformed body afterwards, then through solidification, acidleach (structure uneven surface), take out, fiber-reinforced epoxy resin-based composite material super-hydrophobic surface is obtained after drying and finishing (low surface energy molecule).This invention operating procedure is more complicated, is unfavorable for on-the-spot large-area construction.And the unimolecular layer weathering resistance of finishing is poor.
Chinese invention patent publication number 101575478A discloses a kind of preparation method of epoxy resin super-hydrophobic coat, silica dioxide granule is dissolved in solvent by the method, add silane coupling agent, epoxy resin, hydrophobizing agent obtain coating sol, then uniform application is at substrate surface, finally heating makes epoxy resin cure be cross-linked, and namely obtains epoxy resin super-hydrophobic coat.The coating that the method obtains has good super-hydrophobicity, but the method solidification value is too high, is difficult to big area practical application.Certainly, its physical strength is also very limited.
The super-hydrophobic coat formed by prior art has the shortcoming of bad mechanical property (as hardness, sticking power, shock-resistance, resistance to soft frictional property).
In addition, the existing method for the formation of super-hydrophobic coat has complex process, coating curing temperatures crosses the shortcomings such as high.
Summary of the invention
For above shortcoming, the object of the invention is to, the super-hydrophobic coat a kind of super hydrophobic coating composition being provided and being formed with it, by the coating that this super hydrophobic coating composition is formed, there is excellent ultra-hydrophobicity and the mechanical property of raising.
For realizing object of the present invention, the present invention includes the following content:
[1] a two-pack super hydrophobic coating composition, described super hydrophobic coating composition is made up of component A and B component, wherein,
Component A comprises surface with hydroxyl, amino, epoxy group(ing) or their combination as the inorganic particle of reactive group, hydrophobically modified epoxy resin and epoxy resin toughener; And
B component comprises solidifying agent.
[2] the super hydrophobic coating composition Gen Ju [1], wherein, described inorganic particle comprise in the group being selected from and being made up of the following one or more: titanium dioxide, calcium carbonate, zinc oxide, silicon-dioxide, kaolin, clay and aluminum oxide.
[3] the super hydrophobic coating composition Gen Ju [1], wherein, described inorganic particle is red bayberry structured particles.
[4] the super hydrophobic coating composition Gen Ju [1], wherein, the particle diameter of described inorganic particle is 10nm-40 μm.
[5] the super hydrophobic coating composition Gen Ju [1], wherein, the epoxy resin of hydrophobically modified described in component A is formed by epoxy resin being carried out hydrophobically modified with hydrophobizing agent.
[6] the super hydrophobic coating composition Gen Ju [5], wherein, described epoxy resin comprises one or more in the group being selected from and being made up of the following: glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic based epoxy resin.
[7] the super hydrophobic coating composition Gen Ju [6], wherein, described glycidyl ether type epoxy resin is bisphenol A type epoxy resin.
[8] the super hydrophobic coating composition Gen Ju [5], wherein, described hydrophobizing agent is one or more fluoro-resin.
[9] the super hydrophobic coating composition Gen Ju [8], wherein, described fluoro-resin is fluorocarbon resin or fluorine silicon resin.
[10] the super hydrophobic coating composition Gen Ju [1], wherein, in component A, the weight ratio of described inorganic particle and hydrophobically modified epoxy resin is 1:1 to 1:10.
[11] the super hydrophobic coating composition Gen Ju [1], wherein, component A is also containing defoamer, anti-settling agent, pigment or their combination.
[12] the super hydrophobic coating composition Gen Ju [1], wherein, described solidifying agent comprises one or more in the group being selected from and being made up of the following: quadrol, phenolic aldehyde amine, hexanediamine, mphenylenediamine, polymeric amide, isophorone diamine, Tetra hydro Phthalic anhydride and amine additives thereof.
[13] the super hydrophobic coating composition Gen Ju [1], wherein, B component is also containing promotor.
[14] a kind of super-hydrophobic coat used according to the super hydrophobic coating composition formation according to any one of [1] to [13].
From foregoing, the present invention adopts mechanical property is high, sticking power good, cure shrinkage is low hydrophobically modified epoxy resin as matrix resin, particle is firmly sticked together, obtain the coarse structure with some strength, and utilize another prerequisite that the low surface energy character of the hydrophobizing agents such as fluoro-resin provides super-hydrophobic.Particle surface with hydroxyl, amino, epoxy group(ing) or their combination as reactive group.These groups can with the reactions such as the hydroxyl on the epoxy group(ing) of epoxy resin and fluoro-resin, thus particle is connected on resin securely.Therefore, the physical strength of super-hydrophobic coat is improved.Such as, its ability soft cloth wiping back and forth, in other words, after with soft cloth back and forth wiping, ultra-hydrophobicity declines not obvious, and this is significant for practical application.
The reactive group of described particle surface comprises hydroxyl, amino, epoxy group(ing) or their combination.In inorganic particle production building-up process, inherently can, with hydroxyl, if amino or epoxy group(ing) isoreactivity group, then the particle with the organic substance effects on surface with amino or epoxy group(ing) is hydroxyl be needed to carry out modification gained.Such as, amino modified reaction formula is as shown in Figure 4, and epoxide modified similar.
In the present invention, hydrophobizing agent is one or more fluoro-resin.Fluoro-resin can be fluorocarbon resin or fluorine silicon resin.The resin that fluorocarbon resin is is skeleton with firmly C-F key, with other resin-phase ratios, its thermotolerance, chemical-resistant, winter hardiness, low temperature flexibility, weathering resistance and electrical property etc. are all better.Fluorine silicon resin is the mixing synthetic resins of fluoro-resin and silicone resin.Because fluorocarbon resin or fluorine silicon resin are greater than 90 ° to water contact angle, they can as hydrophobizing agent.
Epoxy resin toughener is used, to improve the toughness of coating in the present invention.This is because epoxy resin itself shows as fragility.
Epoxy resin toughener used can be such as, CYH-277 (Wu great Sen Mao Fine Chemical Co., Ltd, technical grade).If the amount of toughner is too low, toughness is improved not enough.If the amount of toughner is too high, then causes hardness inadequate, show as coating too soft.
In the present invention, solidifying agent is used, for the solidification of epoxy resin.Typical solidifying agent is conventional epoxy curing agent polymeric amide and phenolic aldehyde amine.
In the present invention for preparation coating composition uses solvent.Solvent can be the common solvent for epoxy resin.
In coating composition of the present invention, optionally can also have auxiliary agent for improving coating composition as promotor, defoamer, anti-settling agent, flow agent etc.In addition, pigment can also be contained.
Accompanying drawing explanation
Fig. 1 is showing scanning electron microscopy picture and the water contact angle state graph thereof of the surface microstructure of the epoxy resin-matrix super-hydrophobic coat obtained according to the present invention.
Fig. 2 is showing the scanning electron microscopy picture of the surface microstructure of red bayberry structured particles.
Fig. 3 is the schematic diagram of red bayberry particle preparation method.
Fig. 4 is the schematic diagram amino modified to particle surface.
Embodiment
[coating composition]
Particularly, double-component paint composition of the present invention is made up of component A and B component.Wherein, component A comprises surface with hydroxyl, amino, epoxy group(ing) or their combination as the inorganic particle of reactive group, hydrophobically modified epoxy resin and epoxy resin toughener; B component comprises solidifying agent.
<A component >
Component A comprises the inorganic particle of responding property of surface band group hydroxy or amino, hydrophobically modified epoxy resin and epoxy resin toughener.
Prepare component A by the following method.
A) by median size be 10nm-40 μm be selected from one or more Granular composite in titanium dioxide, calcium carbonate, zinc oxide, silicon-dioxide, kaolin, clay and aluminum oxide etc. in appropriate solvent.Described particle can be that (Raspberry-like, as shown in Figure 2) particle, this granule-morphology is conducive to realizing object of the present invention red bayberry structure.Such as, the silicon dioxide granule of red bayberry structure is that silicon oxide pellets is grafted to the large ball surface formation of silicon-dioxide by chemical reaction.
Solvent herein can be acetone, toluene, dimethylbenzene, pimelinketone, propyl carbinol, ethyl acetate, butylacetate, propylene glycol etc. or their combination; Preferred butylacetate, propyl carbinol, dimethylbenzene or their combination.
B) be dissolved in appropriate solvent by one or more epoxy resin such as Racemic glycidol ethers, glycidyl ester class, Racemic glycidol amine, the alicyclic ring same clan and epoxy resin toughener, then adding hydrophobizing agent modifies, and obtains the epoxy resin of hydrophobically modified.The preferred glycidyl ether type epoxy resin of described epoxy resin, more preferred bisphenol A type epoxy resin.Hydrophobizing agent herein can be fluoro-resin, its specific examples comprises the GK-570 of great Jin, the FY-F535C of Guangzhou Fu Yuangui Science and Technology Ltd., CC1-3 and CC1-4 of Jiaxing Kai Rui Science and Technology Ltd., the WF-Q212 of Rich coating Chemical Industry Co., Ltd. of Wuxi ten thousand, the fluoro-resin in middleization granary etc. one or more.The example of epoxy resin toughener comprises CYH-277 (Wu great Sen Mao Fine Chemical Co., Ltd, technical grade).Solvent herein can be acetone, toluene, dimethylbenzene, pimelinketone, ethyl acetate, butylacetate, propylene glycol, propyl carbinol, methylene dichloride etc. or their combination.
C) being added by the particle suspension liquid of b) step in the hydrophobically modified epoxy resin solution of a) step and to be uniformly dispersed, make to link together between particle and resin, wherein particle and resin content ratio are 1:1 to 1:10.Resin content refers to the content of epoxy resin and fluorine carbon/fluorine silicon resin sum herein.When content ratio is greater than 1:1, there is powder phenomenon-tion in coating, and physical strength declines; When content ratio is less than 1:10, coatingsurface does not form certain coarse structure, cannot realize ultra-hydrophobicity.Super going beyond the scope cannot obtain having the super-hydrophobic coat of good mechanical properties.Optionally, appropriate auxiliary agent can be added.The toning different according to user can also need and add pigment.After filtering with 40-100 order, the filtrate obtained is component A.
By the consumption of epoxy resin as a reference, be chosen to be 100 parts, other proportionings are as shown in table 1 below relative to the content range of content of epoxy resin.
Table 1A amounts of components scope
| Lower limit (weight part) | The upper limit (weight part) | |
| Particle | 10 | 50 |
| The solvent of discrete particles | 30 | 400 |
| Epoxy resin toughener | 20 | 80 |
| Hydrophobizing agent | 300 | 600 |
| The solvent of dissolved epoxy | 100 | 200 |
<B component >
B component comprises solidifying agent.
Prepare B component by the following method.
By one or more solidifying agent such as quadrol, phenolic aldehyde amine, hexanediamine, mphenylenediamine, polymeric amide, isophorone diamine, Tetra hydro Phthalic anhydride and amine additives thereof, preferred polyamide and phenolic aldehyde amine, be dissolved in one or more mixed solvents such as appropriate acetone, toluene, dimethylbenzene, pimelinketone, propyl carbinol, ethyl acetate, butylacetate, propylene glycol, preferred propyl carbinol, dimethylbenzene and butylacetate, after being uniformly mixed, obtain B component.
Based on 100 parts by weight epoxy resin, the amount ranges of solidifying agent and solvent is as shown in table 2 below.
Table 2B amounts of components scope
| Lower limit (weight part) | The upper limit (weight part) | |
| Solidifying agent | 10 | 50 |
| Solvent | 10 | 50 |
< coating composition >
After A, B component are mixed with the weight ratio of 3:1-15:1, i.e. obtained two-pack super hydrophobic coating composition of the present invention.Consider resin and solidifying agent ratio requirement, exceed the performance that this scope will affect coating.
[formation of coating]
Super hydrophobic coating of the present invention when constructing to material surface, must dewater to material surface, oil removing, scrubbing and processing of rust removing.Herein, construction substrate and coated substrate can be glass, metal, wood, stone material etc., as long as be insoluble to organic solvent.
Super hydrophobic coating of the present invention when constructing to material surface, must dewater to material surface, oil removing, scrubbing and processing of rust removing.
Super hydrophobic coating of the present invention can be constructed with brushing, dipping, spin coating or spraying method.Preferred spraying application.The spraying method of super hydrophobic coating of the present invention is: spray under 0.1-0.4MPa, sprays under preferred 0.2-0.3MPa, and spray gun and construction substrate are 70-90 ° of angle, and both distances are 5-30cm, by paint spay-coating in construction substrate surface.
To coat the base material of coating at room temperature to 130 DEG C solidification 1-24h, preferred 40-100 DEG C solidification 2-16h, namely gained coating has ultra-hydrophobicity.Such as, its surface tissue and water contact angle are as shown in Figure 1.
[embodiment]
Below with reference to embodiment, in more detail the present invention is described.But the invention is not restricted to these embodiments.
The epoxy resin used in an embodiment comprises: epoxy resin E-44 (three wooden groups, technical grade), epoxy resin E-51 (Wuxi resin processing plant)
The fluoro-resin used in an embodiment comprises: GK-570 (great Jin), FY-F535C (Guangzhou Fu Yuangui Science and Technology Ltd.), CC1-3 (Jiaxing Kai Rui Science and Technology Ltd.), CC1-4 (Jiaxing Kai Rui Science and Technology Ltd.), WF-Q212 (Rich coating Chemical Industry Co., Ltd. of Wuxi ten thousand), fluoro-resin F0 (middleization granary).
The epoxy resin toughener used in an embodiment is epoxy resin toughener CYH-277 (Wu great Sen Mao Fine Chemical Co., Ltd, technical grade).
The micro-nano granules used in an embodiment comprises: (the self-control of red bayberry structured particles, see accompanying drawing 2, surface is with hydroxyl), clay (Nanocor company, 15-20 μm, surface is with amino), silicon-dioxide (Jiangxi Hua Derun Fine Chemical Works, 100nm, surface is with hydroxyl)
The solidifying agent used in an embodiment comprises: polymeric amide SF650 (mountain peak, Changzhou Chemical Co., Ltd., technical grade), phenolic aldehyde amine T-31 (A) (mountain peak, Changzhou Chemical Co., Ltd., technical grade).
The solvent used in an embodiment comprises: propyl carbinol (Jiangsu Tong Sheng chemical reagent company limited, technical grade), dimethylbenzene (Jiangsu Tong Sheng chemical reagent company limited, technical grade), butylacetate (Jiangsu Tong Sheng chemical reagent company limited, technical grade)
The auxiliary agent used in an embodiment has: altax P-30 (mountain peak, Changzhou Chemical Co., Ltd., technical grade), defoamer BYK-141 (Bi Ke chemistry), anti-settling agent BYK-410 (Bi Ke chemistry)
Preparation example 1: the preparation of red bayberry particle
As shown in Figure 3, bead and the large ball of 1000 ± 200nm of 100 ± 20nm is prepared by the Stober sol-gel method of classics, simply, TEOS is joined containing strong aqua, in aqueous ethanolic solution, 2-6h is reacted at 40 DEG C, silica spheres can be obtained, then modifying the less silicon dioxide granule of 1-5g particle diameter by 0.1-0.6g Silane coupling agent KH550 (NanJing Shuguang Chemical Group Co., Ltd.) (utilizes the hydroxyl of the alkoxyl group on KH550 and silica sphere to carry out polycondensation at 40 DEG C, amino group in grafting), 0.1-0.3g silane coupling agent KH560 (Hangzhou boiling point Chemical Co., Ltd.) is similarly used to modify the larger silicon dioxide granule of 1-5g particle diameter, cycloalkyl groups in grafting, and two kinds of particles are put into xylene solvent again disperse, 2-6h is reacted in the oil bath being placed in 60-80 DEG C, last filtration washing obtains the silicon dioxide granule with red bayberry structure.
Embodiment 1:
The red bayberry structured particles that 5.12g is obtained in preparation example 1 is dispersed in 15.10g propyl carbinol, obtains inorganic particle suspensions.5.06g epoxy resin E-44 and 2.11g epoxy resin toughener CYH-277 are dissolved in the mixed solvent (mass ratio is 1:1) of 5.03g propyl carbinol and dimethylbenzene, then 4.11gWF-Q212,1.98gFY-F535C and 10.01gCC1-3 are joined in obtained epoxy resin solution, stirring reaction 2h at 40 DEG C, obtains the epoxy resin of hydrophobically modified.Then join in the epoxy resin solution of hydrophobically modified by inorganic particle suspensions, add 0.21g defoamer BYK-141 and 0.23g anti-settling agent BYK-410, the filtrate obtained after filtering with 40-100 order is component A.
5.14g polymeric amide SF650 is dissolved in the mixed solvent (mass ratio 1:1) of 4.96g propyl carbinol and dimethylbenzene, adds 0.15g altax P-30, obtain B component.
Component A and B component are mixed with 5:1 (weight ratio), brushes dewatering, oil removing, on tinplate after rust cleaning, then self-vulcanizing 24h, obtains super-hydrophobic coat, and performance is as shown in the table.
The performance of table 3 embodiment 1 gained coating
Embodiment 2:
2.25g clay and 1.15g silicon-dioxide are dispersed in butylacetate (15.11g) solution containing 0.25g BYK-110 dispersion agent, obtain inorganic particle suspensions.5.07g epoxy resin E-51 and 1.51g toughening agent C YH-277 is dissolved in 5.06g dimethylbenzene, then join in obtained epoxy resin solution by changing granary fluoro-resin in 10.13gCC1-4 and 9.97g, stirring reaction 2h at 40 DEG C, obtains the epoxy resin of hydrophobically modified.Then join in the epoxy resin solution of hydrophobically modified by inorganic particle suspensions, the filtrate obtained after filtering with 40-100 order is component A.
2.08g phenolic aldehyde amine T-31 (A) is dissolved in 2.21g dimethylbenzene, adds 0.21g altax P-30, obtain B component.
Component A and B component are mixed with 13:1 (weight ratio), be sprayed under 0.2-0.3MPa with spray gun dewater, oil removing, on tinplate after rust cleaning, then be placed in 80 DEG C of baking oven for drying solidification 1h, obtain super-hydrophobic coat, performance is as shown in the table.
The performance of table 4 embodiment 2 gained coating
Embodiment 3:
4.97g red bayberry structured particles is dispersed in 14.93g butylacetate, obtains inorganic particle suspensions.5.03g epoxy resin E-44 and 3.11g epoxy resin toughener CYH-277 are dissolved in 5.03g dimethylbenzene, then join in obtained epoxy resin solution by changing granary fluoro-resin in 5.07g GK-570,1.98gCC1-3 and 8.01g, stirring reaction 2h at 40 DEG C, obtains the epoxy resin of hydrophobically modified.Then joined by inorganic particle suspensions in the epoxy resin solution after hydrophobically modified, the filtrate obtained after filtering with 40-100 order is component A.
1.55g phenolic aldehyde amine T-31 (A) is dissolved in 2.21g dimethylbenzene, adds 0.23g altax P-30, obtain B component.
Component A and B component are mixed with 12:1 (weight ratio), be sprayed under 0.2-0.3MPa with spray gun dewater, oil removing, on tinplate after rust cleaning, then be placed in 70 DEG C of baking oven for drying solidification 3h, obtain super-hydrophobic coat, performance is as shown in the table.
The performance of table 5 embodiment 3 gained coating
From the embodiment result shown in table 3-5, the super-hydrophobic coat utilizing super-hydrophobic coat composition of the present invention to be formed has excellent ultra-hydrophobicity and the mechanical property of raising.
Claims (14)
1. a two-pack super hydrophobic coating composition, described super hydrophobic coating composition is made up of component A and B component, wherein,
Component A comprises surface with hydroxyl, amino, epoxy group(ing) or their combination as the inorganic particle of reactive group, hydrophobically modified epoxy resin and epoxy resin toughener; And
B component comprises solidifying agent.
2. super hydrophobic coating composition according to claim 1, wherein, described inorganic particle comprise in the group being selected from and being made up of the following one or more: titanium dioxide, calcium carbonate, zinc oxide, silicon-dioxide, kaolin, clay and aluminum oxide.
3. super hydrophobic coating composition according to claim 1, wherein, described inorganic particle is red bayberry structured particles.
4. super hydrophobic coating composition according to claim 1, wherein, the particle diameter of described inorganic particle is 10nm-40 μm.
5. super hydrophobic coating composition according to claim 1, wherein, the epoxy resin of hydrophobically modified described in component A is formed by epoxy resin being carried out hydrophobically modified with hydrophobizing agent.
6. super hydrophobic coating composition according to claim 5, wherein, described epoxy resin comprises one or more in the group being selected from and being made up of the following: glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic based epoxy resin.
7. super hydrophobic coating composition according to claim 6, wherein, described glycidyl ether type epoxy resin is bisphenol A type epoxy resin.
8. super hydrophobic coating composition according to claim 5, wherein, described hydrophobizing agent is one or more fluoro-resin.
9. super hydrophobic coating composition according to claim 8, wherein, described fluoro-resin is fluorocarbon resin or fluorine silicon resin.
10. super hydrophobic coating composition according to claim 1, wherein, in component A, the weight ratio of described inorganic particle and hydrophobically modified epoxy resin is 1:1 to 1:10.
11. super hydrophobic coating compositions according to claim 1, wherein, component A is also containing defoamer, anti-settling agent, pigment or their combination.
12. super hydrophobic coating compositions according to claim 1, wherein, described solidifying agent comprises one or more in the group being selected from and being made up of the following: quadrol, phenolic aldehyde amine, hexanediamine, mphenylenediamine, polymeric amide, isophorone diamine, Tetra hydro Phthalic anhydride and amine additives thereof.
13. super hydrophobic coating compositions according to claim 1, wherein, B component is also containing promotor.
14. 1 kinds of super-hydrophobic coats using the super hydrophobic coating composition according to any one of claim 1 to 13 to be formed.
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| CN106632882A (en) * | 2016-10-01 | 2017-05-10 | 浙江科技学院 | Preparation method of fluorine-containing cation acrylate resin cathode electrophoresis paint |
| CN106947363A (en) * | 2017-04-26 | 2017-07-14 | 吉林大学 | A kind of Biomimetic membranes of super-hydrophobic automatic cleaning high temperature resistant low thermal resistance and preparation method thereof |
| CN107189626A (en) * | 2017-06-01 | 2017-09-22 | 冯智勇 | A kind of epoxide resin protective paint coating |
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| CN109825165A (en) * | 2019-01-30 | 2019-05-31 | 中国人民解放军国防科技大学 | Wear-resistant super-hydrophobic coating and preparation method thereof |
| CN109943200A (en) * | 2019-04-19 | 2019-06-28 | 青岛环普节能科技有限公司 | Old pump transformation super hydrophobic coating of one kind and its preparation method and application |
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| CN112876914A (en) * | 2021-01-14 | 2021-06-01 | 浙江中财管道科技股份有限公司 | Scale-inhibiting super-hydrophobic coating for outer surface of water tank sizing sleeve and preparation method thereof |
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| CN114316797A (en) * | 2021-12-31 | 2022-04-12 | 华为数字能源技术有限公司 | Super-hydrophobic coating, circuit board, electronic device and waterproof device |
| CN115820081A (en) * | 2022-11-15 | 2023-03-21 | 华南理工大学 | Preparation method of water-based super-hydrophobic epoxy resin and application of water-based super-hydrophobic epoxy resin in marine corrosion prevention |
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| CN106632882A (en) * | 2016-10-01 | 2017-05-10 | 浙江科技学院 | Preparation method of fluorine-containing cation acrylate resin cathode electrophoresis paint |
| CN106632882B (en) * | 2016-10-01 | 2019-10-11 | 浙江科技学院 | The preparation method of fluorine-containing cationic acrylate cathode electrophoresis dope |
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| CN111440511A (en) * | 2020-05-11 | 2020-07-24 | 韩永洲 | High-thermal-conductivity nano Al2O3Modified epoxy resin super-hydrophobic coating and preparation method thereof |
| CN111440511B (en) * | 2020-05-11 | 2021-07-13 | 韩永洲 | High-thermal-conductivity nano Al2O3Modified epoxy resin super-hydrophobic coating and preparation method thereof |
| CN112876914A (en) * | 2021-01-14 | 2021-06-01 | 浙江中财管道科技股份有限公司 | Scale-inhibiting super-hydrophobic coating for outer surface of water tank sizing sleeve and preparation method thereof |
| CN114106294A (en) * | 2021-12-13 | 2022-03-01 | 华东理工大学 | Modified epoxy resin and preparation method and application thereof |
| CN114106294B (en) * | 2021-12-13 | 2023-03-03 | 华东理工大学 | Modified epoxy resin and preparation method and application thereof |
| CN114316797A (en) * | 2021-12-31 | 2022-04-12 | 华为数字能源技术有限公司 | Super-hydrophobic coating, circuit board, electronic device and waterproof device |
| CN115820081A (en) * | 2022-11-15 | 2023-03-21 | 华南理工大学 | Preparation method of water-based super-hydrophobic epoxy resin and application of water-based super-hydrophobic epoxy resin in marine corrosion prevention |
| CN115820081B (en) * | 2022-11-15 | 2024-05-17 | 华南理工大学 | Preparation method of water-based super-hydrophobic epoxy resin and application of water-based super-hydrophobic epoxy resin in marine corrosion prevention |
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