CN110922887B - Super-hydrophobic ultraviolet curing coating and preparation method thereof - Google Patents
Super-hydrophobic ultraviolet curing coating and preparation method thereof Download PDFInfo
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- CN110922887B CN110922887B CN201911280563.XA CN201911280563A CN110922887B CN 110922887 B CN110922887 B CN 110922887B CN 201911280563 A CN201911280563 A CN 201911280563A CN 110922887 B CN110922887 B CN 110922887B
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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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
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- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
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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
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- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses an ultraviolet curing coating which comprises the following components in parts by weight: 10-20 parts of fluorine-containing acrylate polymer, 30-45 parts of light curing resin, 30-40 parts of acrylate active monomer, 3-10 parts of photoinitiator, 0.5-5 parts of coupling agent, 0.3-1 part of flatting agent and 0.5-8 parts of lotus leaf powder. The lotus leaf powder is added into the ultraviolet curing coating, the ultra-strong hydrophobicity of the lotus leaf powder is utilized, and the lotus leaf powder is combined with the fluorine-containing acrylate polymer and the light curing resin, so that the hydrophobicity of the coating can be increased, the water contact angle of a cured coating is larger than 150.0 degrees, a lotus leaf effect is formed, the super-hydrophobic coating is formed, the hydrophobic and anti-fouling capability of the cured coating is improved, and the problems of non-transparency and poor strength of a colloid caused by adding too much fluorine or silicon into the coating are solved. The invention also discloses a preparation method of the ultraviolet curing coating.
Description
Technical Field
The invention relates to a coating, in particular to an ultra-hydrophobic ultraviolet curing coating and a preparation method thereof.
Background
A superhydrophobic coating refers to a coating where the contact angle of a water droplet on the surface is greater than 150.0 °, which is related to the chemical composition and the micro-geometry of the solid surface. For the self-cleaning and stain-resistant functions of the UV photocureable coating, a common method is to introduce a silicon or fluorine structure with low surface tension into a molecular structure, but the coating obtained by the method has low water contact angle and cannot meet the requirement of super-hydrophobicity.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a super-hydrophobic ultraviolet fast curing (water drop angle is more than 150.0 degrees) coating and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the ultraviolet curing coating comprises the following components in parts by weight: 10-20 parts of fluorine-containing acrylate polymer, 30-45 parts of light curing resin, 30-40 parts of acrylate active monomer, 3-10 parts of photoinitiator, 0.5-5 parts of coupling agent, 0.3-1 part of flatting agent and 0.5-8 parts of lotus leaf powder.
The ultra-hydrophobic characteristic which can not be met by the UV coating containing fluorine or organic silicon is added, the ultra-strong hydrophobicity of the lotus leaf powder is utilized, the lotus leaf powder is combined with the fluorine-containing acrylate polymer and the photocuring resin, the hydrophobicity of the coating can be increased, the water contact angle of a cured coating is larger than 150.0 degrees, a lotus leaf effect is formed, the ultra-hydrophobic coating is formed, the hydrophobic and anti-fouling capability of the cured coating is improved, and the problems of colloid opaqueness and poor strength caused by adding too much fluorine or silicon in the coating are solved.
As a preferred embodiment of the uv curable coating of the present invention, the lotus leaf powder is modified lotus leaf powder, and the modification method is: the lotus leaf powder and the flatting agent are evenly mixed and then evenly mixed with the coupling agent. According to the modification, the characteristic that the leveling agent can migrate to the surface of a paint film is utilized, the lotus leaf powder is coated by the leveling agent and then is externally protected by the coupling agent, and after the lotus leaf powder is modified by adopting the method, the lotus leaf powder can be enriched on the surface of a colloid, so that a higher water contact angle is achieved.
As a preferred embodiment of the uv curable coating of the present invention, the modification method is: the lotus leaf powder and the flatting agent are mixed and ultrasonically dispersed for 2-4 hours, then the coupling agent is added and uniformly stirred, and the lotus leaf powder is used after being placed for 3-5 hours. By adopting the method, the coupling agent can be fully wetted and coated with the lotus leaf powder and the flatting agent, and the lotus leaf powder modified substance with better quality is prepared.
As a preferred embodiment of the uv curable coating of the present invention, the leveling agent is at least one of an organosilicon leveling agent, an acrylate leveling agent, and a modified acrylate leveling agent. As a more preferred embodiment of the uv curable coating of the present invention, the leveling agent is an organosilicon leveling agent. As a preferred embodiment of the uv curable coating of the present invention, the silicone leveling agent is a reactive group connected to one or both ends of a siloxane chain or the end of an organic modifying group; the reactive group is at least one of a primary hydroxyl group, a vinyl group, an epoxy group and an isocyanate group.
In a preferred embodiment of the uv curable coating of the present invention, the leveling agent is 0.3 to 1 part by weight. The flatting agent in the weight part can realize the migration of the lotus leaf powder to achieve a better hydrophobic effect. More preferably, the leveling agent is 0.4 to 0.8 parts by weight.
As a preferred embodiment of the uv curable coating material of the present invention, the coupling agent is at least one of KH550, KH560 and KH 570.
As a preferable embodiment of the ultraviolet curing coating, the coupling agent is 0.8-3 parts by weight.
As a preferred embodiment of the uv curable coating of the present invention, the fluoroacrylate polymer is a polyurethane acrylate containing a perfluoropolyether structure.
As a preferred embodiment of the uv curable coating of the present invention, the method for preparing the fluoroacrylate polymer comprises the following steps:
(1) dropwise adding an acetone solution of IPDI (isophorone diisocyanate) into perfluoropolyether diol, adding dibutyltin dilaurate, heating to 40-80 ℃, and stirring for reaction for 10-14 h;
(2) and (3) after cooling, dropwise adding an acetone solution of hydroxyethyl methacrylate, heating to 40-80 ℃, stirring for reacting for 6-10 h, and removing the solvent to obtain the fluorine-containing acrylate polymer.
The molecular weight of the perfluoropolyether diol as a preferred embodiment of the ultraviolet curing coating is 1000-1500.
As a preferred embodiment of the UV-curable coating, the molar ratio of-NCO in IPDI and-OH in perfluoropolyether diol is: -NCO ═ OH ═ 1.5-2.5: 1.
As a preferred embodiment of the UV-curable coating, the molar ratio of-NCO in the IPDI and-OH in the hydroxyethyl methacrylate is as follows: -NCO: -OH ═ 1-1.5: 1.
As a preferred embodiment of the uv curable coating of the present invention, in the step (1) and the step (2), the temperature increase rate of the temperature increase is: 0.4-0.6 ℃/min.
In a preferred embodiment of the ultraviolet curing coating, the addition amount of the dibutyltin dilaurate is 0.1-3% of the total mass of the perfluoropolyether diol and the IPDI.
As a preferred embodiment of the uv curable coating of the present invention, the photocurable resin is at least one of urethane acrylate, epoxy acrylate, and polyester acrylate.
As a preferred embodiment of the uv curable coating of the present invention, the acrylate reactive monomer is at least one of isooctyl acrylate, isobornyl acrylate, hydroxyethyl acrylate, 2-phenoxyethyl acrylate, cyclotrimethylolpropane formal acrylate, tetrahydrofurfuryl acrylate, lauryl acrylate, 1, 6-hexanediol diacrylate, ethoxylated bisphenol a diacrylate, pentaerythritol triacrylate, and trimethylolpropane trimethacrylate.
In a preferred embodiment of the uv curable coating of the present invention, the photoinitiator is at least one of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxy-cyclohexyl-phenyl-methanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzylphenyl) butanone, and phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide.
As a preferable embodiment of the ultraviolet curing coating, the lotus leaf powder has a particle size of less than or equal to 50 microns.
As a preferable embodiment of the ultraviolet curing coating, the lotus leaf powder is 2-8 parts by weight. When the adding amount of the lotus leaf powder is more than 8 parts by weight, the contact angle is reduced, so that the lotus leaf powder has better hydrophobic property when being 2-8 parts by weight.
As a more preferable embodiment of the ultraviolet curing coating, the lotus leaf powder is 4-8 parts by weight.
The invention also aims to provide a preparation method of the ultraviolet curing coating, which is characterized by comprising the following steps:
s1, mixing the fluorine-containing acrylate polymer, the photo-curing resin and the acrylate active monomer, and stirring for 0.5-2 h;
s2, adding a photoinitiator, and stirring for 2-5 h;
s3, adding a coupling agent, a leveling agent and a lotus leaf powder mixture, and stirring for 1-3 h;
s4, defoaming in vacuum to obtain the ultraviolet curing coating;
the preparation method of the mixture of the coupling agent, the leveling agent and the lotus leaf powder comprises the following steps: the lotus leaf powder and the flatting agent are uniformly mixed, and then the lotus leaf powder and the coupling agent are uniformly mixed to obtain a mixture of the coupling agent, the flatting agent and the lotus leaf powder.
The illumination wave band of the ultraviolet curing coating is preferably 200-760 nm, more preferably 250-500 nm, and most preferably 250-405 nm.
The invention has the beneficial effects that: the invention provides an ultraviolet curing coating. The lotus leaf powder is added into the ultraviolet curing coating, the ultra-strong hydrophobicity of the lotus leaf powder is utilized, and the lotus leaf powder is combined with the fluorine-containing acrylate polymer and the light curing resin, so that the hydrophobicity of the coating can be increased, the water contact angle of a cured coating is larger than 150.0 degrees, a lotus leaf effect is formed, the super-hydrophobic coating is formed, the hydrophobic and anti-fouling capability of the cured coating is improved, and the problems of non-transparency and poor strength of a colloid caused by adding too much fluorine or silicon into the coating are solved.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The raw materials in the following examples are all commercially available general-purpose materials unless otherwise specified. Wherein the polyurethane acrylate is a product of Sandoma chemical Co.Ltd under the brand number CN996 NS; a product of epoxy acrylate sartomer chemical limited under the designation CNUVE151 NS; polyester acrylates are available from sartomer chemical limited under the designation CN2203 NS; the acrylate leveling agent is SN3058/BYK354 produced by Shanghai deep bamboo chemical science and technology Limited.
The lotus leaf powder related in the embodiment is obtained by adopting the following method: grinding the dried lotus leaves into powder, and sieving the powder with a stainless steel mesh sieve with the aperture less than or equal to 50 microns.
Example 1
In an embodiment of the uv curable coating of the present invention, the uv curable coating includes the following components in parts by weight: 15 parts of fluorine-containing acrylate polymer, 40 parts of light-cured resin, 37 parts of acrylate active monomer, 0.7 part of flatting agent, 0.8 part of coupling agent, 5 parts of photoinitiator and 1.5 parts of lotus leaf powder;
wherein the light-cured resin is urethane acrylate; the acrylate active monomer comprises the following components in parts by weight: 20 parts of isobornyl acrylate, 15 parts of isooctyl acrylate and 2 parts of 1, 6-hexanediol diacrylate; the flatting agent is an acrylate flatting agent; the coupling agent is KH550 coupling agent; the photoinitiator consists of the following components in parts by weight: 1 part of 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone and 4 parts of 1-hydroxy-cyclohexyl-phenyl ketone.
The preparation method of the fluorine-containing acrylate polymer comprises the following steps:
1) adding 26g of perfluoropolyether diol with the molecular weight of 1000-1500 into a 250ml dry three-neck flask provided with a reflux condenser tube, a thermometer and a stirring device, stirring at a constant temperature of 38 ℃, and sequentially dropwise adding a mixture dissolved with 164g of IPDI (the molar ratio of-NCO in the IPDI to-OH in the perfluoropolyether diol is as follows: -NCO ═ OH ═ 2:1) in acetone and 0.5g of dibutyltin dilaurate, the temperature was raised from 38 ℃ to 55 ℃ within 30min and the reaction was stirred at constant temperature at 55 ℃ for 12 h;
2) the experiment was cooled to room temperature and 12g of hydroxyethyl methacrylate (the molar ratio of-NCO in IPDI to-OH in said hydroxyethyl methacrylate: and (3) adding an acetone solution of-NCO: -OH ═ 1.1:1), raising the temperature from 38 ℃ to 55 ℃ within 30min, reacting at a constant temperature for 8h, finishing the reaction, and evaporating the solvent after the reaction is finished to obtain the fluorine-containing acrylate polymer.
The preparation method of the ultraviolet curing coating comprises the following steps:
s1, putting a fluorine-containing acrylate polymer, a light-cured resin and an acrylate active monomer into a planetary stirrer, and mixing and stirring for 1 h;
s2, adding a photoinitiator, and stirring for 4 hours;
s3, adding a mixture of a coupling agent, a leveling agent and lotus leaf powder, and putting into a planetary stirrer to stir for 2 hours;
the preparation method of the mixture of the coupling agent, the leveling agent and the lotus leaf powder comprises the following steps:
a. mixing the lotus leaf powder and the flatting agent, and ultrasonically dispersing for 3 hours;
b. adding coupling agent, stirring uniformly, and standing for 4h for immediate use.
And S4, defoaming in vacuum and discharging to obtain the ultraviolet curing coating.
Example 2
In an embodiment of the uv curable coating of the present invention, the uv curable coating includes the following components in parts by weight: 10 parts of fluorine-containing acrylate polymer, 45 parts of light-cured resin, 36 parts of acrylate active monomer, 0.5 part of flatting agent, 1.5 parts of coupling agent, 6.5 parts of photoinitiator and 2.5 parts of lotus leaf powder;
the light-cured resin comprises the following components in parts by weight: 20 parts of urethane acrylate and 25 parts of epoxy acrylate; the acrylate active monomer comprises the following components in parts by weight: 22 parts of 2-phenoxyethyl acrylate, 6 parts of cyclotrimethylolpropane methylal acrylate and 8 parts of isooctyl acrylate; the leveling agent is an organic silicon leveling agent with primary hydroxyl; the coupling agent is KH560 coupling agent; the photoinitiator consists of the following components in parts by weight: 3.5 parts of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone and 3 parts of 1-hydroxy-cyclohexyl-phenyl-methanone.
The preparation method of the fluoroacrylate polymer and the preparation method of the uv-curable coating described in this example are the same as in example 1.
Example 3
In an embodiment of the uv curable coating of the present invention, the uv curable coating includes the following components in parts by weight: 10 parts of fluorine-containing acrylate polymer, 35 parts of light-cured resin, 35 parts of acrylate active monomer, 1 part of flatting agent, 5 parts of coupling agent, 6 parts of photoinitiator and 8 parts of lotus leaf powder;
wherein the light-cured resin is polyester acrylate; the acrylate active monomer is hydroxyethyl acrylate; the leveling agent is an organic silicon leveling agent containing vinyl groups; the coupling agent is KH 570; the photoinitiator consists of the following components in parts by weight: 2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 2 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
The preparation method of the fluoroacrylate polymer and the preparation method of the uv-curable coating described in this example are the same as in example 1.
Example 4
In an embodiment of the uv curable coating of the present invention, the uv curable coating includes the following components in parts by weight: 10 parts of fluorine-containing acrylate polymer, 35 parts of light-cured resin, 34 parts of acrylate active monomer, 1 part of flatting agent, 5 parts of coupling agent, 6 parts of photoinitiator and 8 parts of lotus leaf powder;
the light-cured resin comprises the following components in parts by weight: 10 parts of polyurethane acrylate, 15 parts of epoxy acrylate and 10 parts of polyester acrylate; the acrylate active monomer comprises the following components in parts by weight: 12 parts of tetrahydrofuran acrylate, 10 parts of lauryl acrylate and 12 parts of ethoxylated bisphenol A diacrylate; the leveling agent is an organic silicon leveling agent containing epoxy groups; the coupling agent comprises the following components in parts by weight: 2.5 parts of KH550 coupling agent and 2.5 parts of KH560 coupling agent; the photoinitiator is 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-acetone.
The preparation method of the fluoroacrylate polymer and the preparation method of the uv-curable coating described in this example are the same as in example 1.
Example 5
In an embodiment of the uv curable coating of the present invention, the uv curable coating includes the following components in parts by weight: 18 parts of fluorine-containing acrylate polymer, 38 parts of light-cured resin, 36 parts of acrylate active monomer, 0.3 part of flatting agent, 1.7 parts of coupling agent, 5.5 parts of photoinitiator and 0.5 part of lotus leaf powder;
the light-cured resin comprises the following components in parts by weight: 20 parts of urethane acrylate and 18 parts of epoxy acrylate; the acrylate active monomer comprises the following components in parts by weight: 12 parts of 2-phenoxyethyl acrylate, 16 parts of cyclotrimethylolpropane methylal acrylate and 8 parts of isooctyl acrylate; the leveling agent is an organic silicon leveling agent containing isocyanate groups; the coupling agent comprises the following components in parts by weight: 0.85 part of KH550 coupling agent and 0.85 part of KH570 coupling agent; the photoinitiator consists of the following components in parts by weight: 3.5 parts of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone and 2 parts of 1-hydroxy-cyclohexyl-phenyl ketone.
The preparation method of the uv curable coating of this example is the same as that of example 1, and will not be described in detail.
Example 6
In an embodiment of the uv curable coating of the present invention, the uv curable coating includes the following components in parts by weight: 15 parts of fluorine-containing acrylate polymer, 38 parts of light-cured resin, 37 parts of acrylate active monomer, 0.5 part of flatting agent, 3 parts of coupling agent, 6 parts of photoinitiator and 0.5 part of lotus leaf powder;
the light-cured resin comprises the following components in parts by weight: 20 parts of urethane acrylate and 18 parts of epoxy acrylate; the acrylate active monomer comprises the following components in parts by weight: 22 parts of pentaerythritol triacrylate and 15 parts of trimethylolpropane trimethacrylate; the leveling agent is an organic silicon leveling agent containing isocyanate groups; the coupling agent comprises the following components in parts by weight: 1.5 parts of KH560 coupling agent and 1.5 parts of KH570 coupling agent; the photoinitiator consists of the following components in parts by weight: 4 parts of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone and 2 parts of 1-hydroxy-cyclohexyl-phenyl ketone.
The preparation method of the uv curable coating of this example is the same as that of example 1, and will not be described in detail.
Comparative example 1
The formula of the ultraviolet curing coating of the comparative example is different from that of the example 1 only in that no lotus leaf powder is added in the comparative example.
The preparation method of the ultraviolet curing coating of the comparative example comprises the following steps:
s1, putting a fluorine-containing acrylate polymer, a light-cured resin and an acrylate active monomer into a planetary stirrer, and mixing and stirring for 1 h;
s2, adding a photoinitiator, and stirring for 4 hours;
s3, adding a coupling agent and a leveling agent, and putting into a planetary stirrer to stir for 2 hours;
and S4, defoaming in vacuum and discharging to obtain the ultraviolet curing coating.
Comparative example 2
A comparative example of the uv curable coating according to the present invention, which is different from example 1 only in that no leveling agent is added.
The preparation method of the ultraviolet curing coating of the comparative example comprises the following steps:
s1, putting a fluorine-containing acrylate polymer, a light-cured resin and an acrylate active monomer into a planetary stirrer, and mixing and stirring for 1 h;
s2, adding a photoinitiator, and stirring for 4 hours;
s3, adding a mixture of a coupling agent and lotus leaf powder, and putting the mixture into a planetary stirrer to stir for 2 hours;
the preparation method of the mixture of the coupling agent and the lotus leaf powder comprises the following steps: the coupling agent and the lotus leaf powder are stirred uniformly and are used immediately after being placed for 4 hours.
And S4, defoaming in vacuum and discharging to obtain the ultraviolet curing coating.
Comparative example 3
A comparative example of the uv curable coating according to the present invention, which was different from example 1 only in that no coupling agent was added.
The preparation method of the ultraviolet curing coating of the comparative example comprises the following steps:
s1, putting a fluorine-containing acrylate polymer, a light-cured resin and an acrylate active monomer into a planetary stirrer, and mixing and stirring for 0.5-2 h;
s2, adding a photoinitiator, and stirring for 2-5 h;
s3, adding a mixture of the leveling agent and the lotus leaf powder, and putting the mixture into a planetary stirrer to stir for 2 hours;
the preparation method of the mixture of the leveling agent and the lotus leaf powder comprises the following steps: mixing the lotus leaf powder and the flatting agent, and ultrasonically dispersing for 3 hours.
And S4, defoaming in vacuum and discharging to obtain the ultraviolet curing coating.
Comparative example 4
A comparative example of the uv curable coating according to the present invention, the formulation of the uv curable coating according to the present comparative example was the same as that of example 1.
The preparation method of the uv curable coating according to this comparative example is different from that of example 1 only in S3, and in this comparative example, the coupling agent, the leveling agent, and the lotus leaf powder are not prepared in advance as a mixture of the coupling agent, the leveling agent, and the lotus leaf powder, that is, the preparation method of the uv curable coating according to this comparative example includes the following steps:
s1, putting a fluorine-containing acrylate polymer, a light-cured resin and an acrylate active monomer into a planetary stirrer, and mixing and stirring for 0.5-2 h;
s2, adding a photoinitiator, and stirring for 2-5 h;
s3, adding a coupling agent, a leveling agent and lotus leaf powder, and putting into a planetary stirrer to stir for 2 hours;
and S4, defoaming in vacuum and discharging to obtain the ultraviolet curing coating.
Example 7
The coatings described in examples 1-6 and comparative examples 1-4 were subjected to glass and glass shear strength tests, and sample pieces with a length and width of 5cm x 5cm were prepared for measuring light transmittance, hardness, water contact angle and water absorption of 270nm-800nm, and the test methods were as follows:
glass & glass shear strength: curing the colloid between glass and glass (colloid thickness 0.15mm) using a UV mercury lamp/LED, and immediately performing a shear strength test; the test standard is GB/T7124;
light transmittance: curing the colloid into sample wafers with the size, length and width of 5cm x 5cm, and then testing the light transmittance with the wavelength of 270nm-800nm by an optical transmittance instrument (LH 1013);
pencil hardness: tested according to ASTM D3363-05(2011) Standard;
water contact angle: tested according to ASTM D5946-2017;
water absorption: after the coating is subjected to ultraviolet curing, 5g of coating is weighed, the coating is placed in purified water and soaked for 24 hours at normal temperature, then the coating is filtered, and the water absorption rate is calculated.
The test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the ultraviolet curing coatings prepared in the embodiments 1-6 of the invention have water contact angles of more than 150 degrees at a wavelength of 270-800 nm, and the coatings have the advantages of super-hydrophobicity, high hardness, high shear strength, low water absorption rate and the like, and have good application prospects. The comparative example 1 is not added with lotus leaf powder, and has low hardness, low water contact angle and high water absorption rate, which shows that the use of lotus leaf powder is beneficial to improving hydrophobicity and reducing water absorption rate; the test results of the comparative examples 2 and 3 show that both the leveling agent and the coupling agent are helpful for improving the hydrophobic property of the coating, and the comparison between the comparative example 4 and the example 1 shows that the lotus leaf powder is mixed and modified with the leveling agent and the coupling agent firstly and then added into the coating to achieve the hydrophobic effect better than that of the lotus leaf powder directly added.
Example 8
In the components of the ultraviolet curing coating, the content of lotus leaf powder influences the performance of the ultraviolet curing coating, in order to investigate the influence of the content of lotus leaf powder on the performance of the ultraviolet curing coating, in the embodiment, except that the content of lotus leaf powder is different from that of embodiment 2, the content of lotus leaf powder in a test group and a control group is the same as that of embodiment 2, and test groups 1 to 11 and control groups 1 to 3 of the ultraviolet curing coating are prepared according to the method of embodiment 2. And the performance of the test group and the control group of the ultraviolet curing coating test group was tested according to the performance test method in example 7. The composition of the uv curable coating and the results of the performance tests are shown in table 2.
TABLE 2
As can be seen from Table 2, with the increase of the using amount of the lotus leaf powder, the hydrophobic property is increased, the transmittance is reduced, the glass shear strength is reduced to some extent, the glass and glass shear strength are reduced to below 1.5MPa, the adhesive force is difficult to meet the requirement, and the Baige knife test result is unqualified; when the addition amount of the lotus leaves exceeds 8 parts, the hydrophobicity is reduced to some extent, the hardness is also reduced, and when the amount of the lotus leaf powder is 0.5-8 parts, the comprehensive performance of the hydrophobicity, the shear strength and the hardness is good, so that the requirement of super-hydrophobicity can be met.
Example 8
In this embodiment, a test set of the uv curable coating is prepared according to the method in example 2, different curing illumination wavelengths are changed, and the performance of the test set of the uv curable coating in example 2 is tested according to the performance testing method in example 7. The compositions and performance test results of the ultraviolet curing coatings of test groups 12-17 are shown in Table 3.
TABLE 3
As can be seen from Table 3, the shear strength, water contact angle and water absorption rate are affected by different wavelengths of light, and the same coating has higher shear strength and low water absorption rate when the wavelength of light is 250-405 nm.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The ultraviolet curing coating is characterized by comprising the following components in parts by weight: 10-20 parts of a fluorine-containing acrylate polymer, 30-45 parts of a photo-curing resin, 30-40 parts of an acrylate active monomer, 3-10 parts of a photoinitiator, 0.5-5 parts of a coupling agent, 0.3-1 part of a leveling agent and 0.5-8 parts of lotus leaf powder, wherein the leveling agent is at least one of an organic silicon leveling agent, an acrylate leveling agent and a modified acrylate leveling agent, the coupling agent is at least one of KH550, KH560 and KH570, and the preparation method of the fluorine-containing acrylate polymer comprises the following steps:
(1) dropwise adding an acetone solution of IPDI (isophorone diisocyanate) into perfluoropolyether diol, adding dibutyltin dilaurate, heating to 40-80 ℃, and stirring for reaction for 10-14 h;
(2) cooling, dropwise adding an acetone solution of hydroxyethyl methacrylate, heating to 40-80 ℃, stirring for reacting for 6-10 h, and removing the solvent to obtain the fluorine-containing acrylate polymer;
the lotus leaf powder is modified lotus leaf powder, and the modification method comprises the following steps: the lotus leaf powder and the flatting agent are evenly mixed and then evenly mixed with the coupling agent.
2. The UV-curable coating according to claim 1, wherein the leveling agent is an organosilicon leveling agent.
3. The ultraviolet-curable coating material according to claim 2, wherein the silicone leveling agent is a reactive group attached to one or both ends of a siloxane chain or to the end of an organic modifying group; the reactive group is at least one of a primary hydroxyl group, a vinyl group, an epoxy group and an isocyanate group.
4. The UV-curable coating according to claim 1, wherein the fluorine-containing acrylate polymer is urethane acrylate containing a perfluoropolyether structure.
5. The UV-curable coating according to claim 1, wherein at least one of the following (a) - (d):
(a) the molecular weight of the perfluoropolyether diol is 1000-1500;
(b) the mole ratio of-NCO in the IPDI and-OH in the perfluoropolyether diol is as follows: -NCO: -OH = 1.5-2.5: 1;
(c) the mol ratio of-NCO in the IPDI and-OH in the hydroxyethyl methacrylate is as follows: -NCO: -OH = 1-1.5: 1;
(d) in the step (1) and the step (2), the heating rate of the temperature rise is as follows: 0.4-0.6 ℃/min.
6. The UV-curable coating according to claim 1, wherein at least one of the following (e) - (g):
(e) the light-cured resin is at least one of polyurethane acrylate, epoxy acrylate and polyester acrylate;
(f) the acrylate active monomer is at least one of isooctyl acrylate, isobornyl acrylate, hydroxyethyl acrylate, 2-phenoxyethyl acrylate, cyclotrimethylolpropane methylal acrylate, tetrahydrofuran acrylate, lauryl acrylate, 1, 6-hexanediol diacrylate, ethoxylated bisphenol A diacrylate, pentaerythritol triacrylate and trimethylolpropane trimethacrylate;
(g) the photoinitiator is at least one of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
7. The ultraviolet-curable coating according to claim 1, wherein the lotus leaf powder is 2 to 8 parts by weight.
8. The UV-curable coating according to claim 7, wherein the lotus leaf powder is 4 to 8 parts by weight.
9. The method for preparing the ultraviolet curing coating of any one of claims 1 to 8, which is characterized by comprising the following steps:
s1, mixing the fluorine-containing acrylate polymer, the photo-curing resin and the acrylate active monomer, and stirring for 0.5-2 h;
s2, adding a photoinitiator, and stirring for 2-5 h;
s3, adding a coupling agent, a leveling agent and a lotus leaf powder mixture, and stirring for 1-3 h;
s4, defoaming in vacuum to obtain the ultraviolet curing coating;
the preparation method of the mixture of the coupling agent, the leveling agent and the lotus leaf powder comprises the following steps: the lotus leaf powder and the flatting agent are mixed uniformly, and then the mixture is mixed uniformly with the coupling agent, so that the mixture of the coupling agent, the flatting agent and the lotus leaf powder is obtained.
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| CN111849343A (en) * | 2020-07-29 | 2020-10-30 | 江苏晶华新材料科技有限公司 | Ultraviolet light curing coating composition and coating process thereof |
| CN112625480B (en) * | 2020-12-02 | 2022-03-04 | 杭州福斯特应用材料股份有限公司 | Photocuring transparent coating |
| CN112762278A (en) * | 2020-12-31 | 2021-05-07 | 湖北本本科技有限公司 | Silicone tube and preparation method thereof |
| CN113755077A (en) * | 2021-07-30 | 2021-12-07 | 武汉格林鸿业新材料科技有限公司 | Hydrophobic anti-fouling ultraviolet curing coating and preparation method thereof |
| CN113969089A (en) * | 2021-11-11 | 2022-01-25 | 上海巴洛特新材料研究有限公司 | Heat-insulating waterproof coating composition for building exterior wall and application method thereof |
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| CN114231159A (en) * | 2021-12-28 | 2022-03-25 | 中天恒泽科技(深圳)有限公司 | UV mirror back coating for glass mirror and preparation method thereof |
| CN115491109B (en) * | 2022-09-15 | 2024-03-01 | 上海金力泰化工股份有限公司 | Fluorine-containing modified acrylic resin photocuring quick repair paint and preparation method and application thereof |
| CN115322690B (en) * | 2022-09-20 | 2023-07-14 | 深圳市金泰科环保线缆有限公司 | TPU (thermoplastic polyurethane) glue for drag chain bonding and doubling, drag chain bonding and doubling and manufacturing method thereof |
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