Self-cleaning wear-resistant uv light-cured coating and preparation method and application thereof

Abstract

The application discloses a kind of self-cleaning wear-resistant UV light curing coating and its preparation method and application.The raw material composition of self-cleaning wear-resistant UV light curing coating includes, by weight parts, acrylate resin 20-95 parts, active diluent 10-60 parts, photoinitiator 0.1-5 parts, solvent 1-20 parts, perfluoropolyether modified long fluorine side chain polyurethane acrylate 0.1-10 parts, leveling agent 0.1-0.5 parts.Perfluoropolyether modified long fluorine side chain polyurethane acrylate gives UV light curing coating excellent hydrophobic and oleophobic, anti-graffiti, anti-fingerprint, smoothness, low refractive and wear-resistant properties, realizes long-term protection of coating surface.The coating surface formed by self-cleaning wear-resistant UV light curing coating has water contact angle not less than 110°, n-hexadecane static oil contact angle not less than 65°, with good antifouling property, fingerprint wiping property, wear resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of ultraviolet (UV) light-cured coatings, in particular to a self-cleaning wear-resistant UV light-cured coating and a preparation method and application thereof. BACKGROUND

[0002] Functional electronic coating material is a kind of polymer film coated on the surface of electronic products and devices such as computers, communications, consumer electronics and 3C, which can protect electronic products and printed circuit boards (PCB) and other devices from corrosion and environmental pollution, thereby enhancing the weather resistance of the product and prolonging the service life, and has been widely used in 3C electronics, aerospace, automotive, military and industrial fields. Functional electronic coating material can be formed by ultraviolet light irradiation of ultraviolet light-cured coating coated on the surface of the substrate. With the advent of the Internet of Things era, the demand for ultraviolet light-cured surface functional coating for electronic products such as chip manufacturing, new display and integrated circuit continues to grow. In addition to providing scratch and wear protection, the coating also needs to have the ability to resist small contaminants such as water, sweat and grease. However, the main resin in the coating composition has a high surface tension, resulting in a high surface energy of the prepared coating, which leads to poor hydrophobic and oleophobicity.

[0003] Ultraviolet light-cured coating is generally composed of main resin, reactive diluent, photoinitiator and additives. Although the amount of additives added is small, high-performance antifouling additives are the key components of the coating composition, which effectively improve the water and oil repellent properties of the coating, and play an important role in the mechanical durability, chemical stability and hydrophobic and oleophobic stability of the coating. Silicone antifouling additives and fluorine antifouling additives are often used to reduce the surface tension of the coating and inhibit the adhesion of dust and fingerprints and other contaminants. However, with the increase of cleaning times, the siloxane compound on the surface of the coating decreases or even disappears completely, and silicone antifouling additives are mostly used for short-term protection. Fluorine antifouling additives have more advantages in terms of light transmission, improvement of hydrophobicity, wear resistance and resistance to small contaminants.

[0004] Perfluoropolyether is a long fluorine chain oligomer with a molecular weight of up to several thousand to tens of thousands. There is widespread attention and application in designing and synthesizing fluorine antifouling additives based on perfluoropolyether. Currently, fluorine antifouling additives based on perfluoropolyether disclosed include "KY-1203" produced by Japan Shin-Etsu Chemical Co., Ltd., "Fluorolink AD1700" and "Fluorolink MD700" produced by Italy Solvay Co., "OPTOOL DAC-HP" produced by Japan Daikin Industrial Co., "RS-90" produced by Japan DIC Co., etc. The use of any one or a combination of at least two of the above in ultraviolet light-cured coating can enhance the hydrophobicity of the coating surface and impart dirt and wear resistance.

[0005] Patent specification with publication number CN109679483A discloses a UV light-cured coating containing perfluoropolyether modified additive and its preparation method and application. The perfluoropolyether modified additive is a copolymer synthesized by free radical polymerization reaction of polyurethane acrylate resin, perfluoropolyether acrylate and acrylate monomer under the action of initiator. This perfluoropolyether modified additive does not contain carbon-carbon double bond, and when added to the UV light-cured coating, it does not participate in the crosslinking reaction of the coating under the irradiation of ultraviolet light (photo-induced polymerization, crosslinking reaction), but only exists in the form of physical blending.

[0006] By comparison, the reactive fluorine-based antifouling additive participates in the crosslinking reaction of the coating film cured by ultraviolet irradiation through double bond, and the antifouling agent is fixed on the surface of the coating in the form of chemical crosslinking, thereby providing long-term protection for the surface of the coating. Patent specification with publication number CN106047090A discloses a perfluoropolyether acrylate composite UV light-cured coating and its preparation method. The perfluoropolyether acrylate composite UV light-cured coating is a reactive fluorine-based antifouling additive, and the double bond-terminated perfluoropolyether acrylate is prepared based on double-end hydroxyl perfluoropolyether. At this time, the perfluoropolyether is located in the main chain structure, and the fluorine-containing segment can migrate during the curing process and produce a fluorine element enrichment effect on the material surface.

[0007] When the perfluoropolyether is located in the side chain, the fluorine segment has better surface migration ability than the main chain structure, and has better surface performance. Therefore, it is of great significance and industrial value to design and synthesize a kind of double bond-terminated reactive fluorine-based antifouling additive with perfluoropolyether side groups, and further improve the hydrophobic and oleophobic properties, wear resistance and other properties of the coating by compounding with other components of the coating. SUMMARY

[0008] The present application provides a self-cleaning wear-resistant UV light-cured coating which can form a film on the surface of plastics, leather, paper, metal, glass and the like, and can endow the coating with excellent hydrophobic and oleophobic properties, high wear resistance, self-cleaning property and the like after ultraviolet irradiation and curing.

[0009] A self-cleaning wear-resistant UV light-cured coating, the raw material composition includes, in weight parts:

[0010]

[0011] The perfluoropolyether modified long fluorine side chain polyurethane acrylate has a structure as shown in formula (I):

[0012]

[0013] In formula (I):

[0014] m and n are integers, 1≤m≤30, 1≤n≤24;

[0015] R1 is selected from the following structures:

[0016]

[0017] R2 is selected from structures (a) to (c):

[0018] (a)

[0019] wherein K is selected from H, F, R' is selected from H, C1-C5 alkyl, p is an integer from 1 to 5, and q is an integer from 1 to 200;

[0020] (b)

[0021] wherein R" is C2-C6 alkyl, and a is an integer from 4 to 17;

[0022] (c)

[0023] wherein b, c, d, f are each independently an integer from 0 to 100, and e is an integer from 3 to 200;

[0024] R3 is in accordance with the following formula:

[0025] G-R f -G'-

[0026] wherein:

[0027] G is selected from -F, -CF2Cl, -CF2CF2Cl, -CF2COOM, and a non-functional straight chain or branched C1-C4 perfluoroalkyl group, and M is selected from the group consisting of cations Na + , K + , Rb + , Cs + ;

[0028] R f is a C1-C5 saturated chain hydrocarbon group containing an ether bond;

[0029]

[0030] wherein g, h, i, j are each independently an integer from 0 to 300, and the sum of g, h, i, j is greater than 5;

[0031] G' is selected from a non-functional straight chain or branched C1-C4 perfluoroalkylene group;

[0032] R a is a C1-C5 saturated chain hydrocarbon group containing an ether bond;

[0033] R b is a C1-C5 alkylene group;

[0034] R4 is in accordance with the following formula:

[0035]

[0036] wherein k is an integer of 1 to 3;

[0037] X is selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 21 carbon atoms;

[0038] Y is selected from the group consisting of O and NH;

[0039] Z is selected from the group consisting of a linear aliphatic group having 1 to 21 (preferably 1 to 11) carbon atoms, an aromatic group having 6 to 10 carbon atoms, and a cyclic aliphatic group having 6 to 10 carbon atoms.

[0040] In the perfluoropolyether-modified long-fluoroside-chain polyurethane acrylate, the repeating units shown in R2may be randomly bonded, and these repeating units can be linear or branched.

[0041] In the perfluoropolyether-modified long-fluoroside-chain polyurethane acrylate, R f The repeating units (CF2O), (C2F4O), (C3F6O), and (C4F8O) shown in R2may be in any order, and these repeating units can be linear or branched.

[0042] In the perfluoropolyether-modified long-fluoroside-chain polyurethane acrylate, in some embodiments, in structure (c), b, c, d, and f can all be greater than 0.

[0043] The number average molecular weight of the perfluoropolyether-modified long-fluoroside-chain polyurethane acrylate can be 1 x 10 3 to 9 x 10 5 g / mol.

[0044] In some embodiments, the static water contact angle of the perfluoropolyether-modified long-fluoroside-chain polyurethane acrylate is greater than 110°, and further not less than 115°, for example, can be 115° to 120°, and the like, and the static oil contact angle with n-hexadecane is greater than 70°, and further not less than 74°, for example, can be 74° to 84°.

[0045] A method for preparing the perfluoropolyether-modified long-fluoroside-chain polyurethane acrylate is provided, comprising the steps of:

[0046] S1, a diisocyanate is subjected to a polymerization reaction with an oligomer diol to obtain a first intermediate product;

[0047] The diisocyanate has a structure shown in formula (II): OCN-R1-NCO (II);

[0048] The oligomer diol has a structure shown in formula (III): HO-R2-OH (III);

[0049] S2, adding a perfluoropolyether derivative with double hydroxyl at one end to the first intermediate product to perform a polymerization reaction, to obtain a second intermediate product;

[0050] The perfluoropolyether derivative with double hydroxyl at one end has a structure as shown in formula (IV):

[0051]

[0052] S3, adding a compound with a structure as shown in formula (V) to the second intermediate product to perform a capping reaction, to obtain the perfluoropolyether modified long fluorine side chain polyurethane acrylate;

[0053] R4-OH (V).

[0054] Step S1 can specifically include: under the conditions of inert atmosphere protection and the presence of an initiator, performing a polymerization reaction of diisocyanate and oligomer diol in a first solvent at 40-100°C until the -NCO group reaches the theoretical content, to obtain a first intermediate product.

[0055] The inert atmosphere refers to a gas atmosphere that does not participate in the reaction, which can be, for example, a nitrogen atmosphere and / or a rare gas atmosphere, etc.

[0056] The initiator can include at least one of dibutyltin dilaurate, azobisisobutyronitrile, and t-butyl peroxide.

[0057] The first solvent can include at least one of acetone, butanone, ethyl acetate, butyl acetate, etc.

[0058] As a preferred, step S1 is performed under anhydrous conditions.

[0059] In step S1, the diisocyanate can be at least one of toluene diisocyanate, isophorone diisocyanate, diphenyl methane diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate, etc. As a preferred, the diisocyanate is isophorone diisocyanate.

[0060] In step S1, the oligomer diol can include polytetrahydrofuran ether diol, etc.

[0061] In step S1, the number average molecular weight of the oligomer diol can be 400-5000 g / mol, and further can be 400-3000 g / mol, for example, can be 1000 g / mol, etc.

[0062] In step S1, the time of the polymerization reaction can be 6-24 hours.

[0063] The antioxidant can be at least one of butylated hydroxytoluene, 2,6-di-tert-butyl-p-cresol, triphenyl phosphate, and sulfurized isobutyl phenol.

[0064] The step S2 can specifically include: adding a perfluoropolyether derivative with double hydroxyl groups at one end into the first intermediate product, and performing a polymerization reaction at 40-100°C until the -NCO group reaches the theoretical content, and then cooling to obtain a second intermediate product.

[0065] The solvent in the perfluoropolyether derivative with double hydroxyl groups at one end can include at least one of 1,2-dichlorotetrafluoroethane, 1,1,2-trifluorotrichloroethane, perfluorobutyl methyl ether, perfluorobutyl ether, p-ditoluene, and trifluorotoluene.

[0066] In the step S2, the perfluoropolyether derivative with double hydroxyl groups at one end can be perfluoropolyether propane 1,2-diol, etc.

[0067] In the step S2, the number average molecular weight of the perfluoropolyether derivative with double hydroxyl groups at one end can be 300-25000 g / mol, further 300-10000 g / mol, and more further 1000-5000 g / mol.

[0068] In the step S2, the polymerization reaction time can be 6-120 hours.

[0069] The step S3 can specifically include: adding a compound with a structure as shown in formula (V) into the second intermediate product, and performing a capping reaction at 40-100°C, and then washing and drying the obtained product after the reaction to obtain the perfluoropolyether modified long fluorine side chain polyurethane acrylate.

[0070] The washing agent used in the washing can be ethanol and diethyl ether.

[0071] The drying can be vacuum drying.

[0072] The drying temperature can be 60-150°C, and the time can be 6-24 hours.

[0073] In the step S3, the compound with a structure as shown in formula (V) can be pentaerythritol triacrylate, etc.

[0074] In the step S3, the capping reaction time can be 6-24 hours.

[0075] In the preparation method of the perfluoropolyether modified long fluorine side chain polyurethane acrylate, the total molar ratio of isocyanate to active hydroxyl groups as reaction raw materials can be 1:1-1.5.

[0076] The present application is based on the perfluoropolyether derivative with double hydroxyl groups at one end, which has excellent properties such as high surface activity, high heat stability, high chemical inertness, hydrophobicity and oleophobicity. By copolymerization with other reactants, the fluorinated polyurethane acrylate with long fluorine side chain, high fluorine element content, good fluorine segment migration ability to the surface, and double bond end-capped reactivity is obtained (i.e. the perfluoropolyether modified long fluorine side chain polyurethane acrylate).

[0077] When the perfluoropolyether modified long fluorine side chain polyurethane acrylate of the present application is used for coating, the water and oil repellency, stain resistance and wear resistance of the coating can be significantly enhanced, and the coating process does not need to be changed. For example, the perfluoropolyether modified long fluorine side chain polyurethane acrylate of the present application is uniformly mixed with acrylate resin, reactive diluent, photoinitiator, solvent, leveling agent, etc. to obtain an ultraviolet (UV) light-curable coating. The coating is formed on the surface of plastic, leather, paper, metal or glass, and is cured by UV irradiation to impart excellent hydrophobicity, oleophobicity, high wear resistance, self-cleaning property and other properties to the coating.

[0078] The perfluoropolyether modified long fluorine side chain polyurethane acrylate of the present application has good reactivity due to the unsaturated group, and can participate in light curing in a light-curable coating system. The urethane bond imparts flexibility and adhesion. The perfluoropolyether long fluorine side chain imparts heat resistance, corrosion resistance (acid, base, oxidizing agent and solvent, etc.), low surface energy, water and oil repellency, electrical insulation, very small friction coefficient, low refractive index and other properties through good fluorine segment migration ability to the surface and fluorine element enrichment. Compared with the reported multifunctional fluorinated polymers, the perfluoropolyether modified long fluorine side chain polyurethane acrylate of the present application exhibits higher hydrophobicity, oleophobicity and stain resistance. At the same time, the prepared UV light-curable coating has excellent water and oil repellency, stain resistance, anti-fingerprint and wear resistance, and also exhibits excellent mechanical stability and chemical stability, which is expected to meet the needs of industrial production.

[0079] The perfluoropolyether modified long fluorine side chain polyurethane acrylate of the present application can be obtained by copolymerization of raw materials including diisocyanate, oligomer diol, perfluoropolyether derivative with double hydroxyl groups at one end, and compound with active hydrogen and acrylate, allyl or vinyl (i.e. compound with structure as shown in formula (V)), wherein the diisocyanate provides the first hard segment part, the oligomer diol provides the soft segment part, the perfluoropolyether derivative with double hydroxyl groups at one end provides the second hard segment part, and the compound with structure as shown in formula (V) can provide unsaturated end groups participating in UV light curing.

[0080] When the perfluoropolyether modified long fluorine side chain polyurethane acrylate of the present application is used for coating, the UV light-curable coating can be endowed with excellent hydrophobicity, oleophobicity, graffiti resistance, fingerprint resistance, smoothness, low refractive index and wear resistance, and long-term protection of the coating surface can be achieved.

[0081] The present application first uses perfluoropolyether derivative with double hydroxyl at one end as a new type of chain extender to copolymerize with isocyanate, hydrogenated or fluorinated polyether or polyester polyol, and unsaturated end group to synthesize multifunctional fluorinated polymer with perfluoropolyether side group (i.e. perfluoropolyether modified long fluorine side chain polyurethane acrylate). Such multifunctional fluorinated polymer has good reactivity and excellent optical properties due to unsaturated groups and urethane bonds, and has excellent properties of fluorine element, such as increasing flexibility of cured coating, reducing stress shrinkage, and improving adhesion.

[0082] The multifunctional fluorinated polymer with perfluoropolyether side group has long fluorine side chain and high fluorine element content, and the main chain can also be introduced with fluorine chain and hydrophobic properties, which are superior to fluorinated polymers including perfluoropolyether derivative only in the main chain and fluorinated polymers with short fluorine chain in the side chain.

[0083] The perfluoropolyether modified long fluorine side chain polyurethane acrylate can improve the migration ability of fluorine segment to the surface, promote the enrichment of fluorine element on the surface, reduce the surface microphase separation, and further improve the hydrophobic and oleophobic properties when applied to coatings and coatings.

[0084] The multifunctional fluorinated polymer with perfluoropolyether side group as an additive added to the coating component can significantly improve the water, oil and dirt resistance, anti-fingerprint and wear resistance of the coating, and achieve long-term protection of the coating surface.

[0085] In some embodiments, the total weight fraction of the acrylate resin, the reactive diluent, the photoinitiator, the solvent, the perfluoropolyether modified long fluorine side chain polyurethane acrylate, and the leveling agent in the raw material composition of the self-cleaning wear-resistant UV light curing coating is 100 parts.

[0086] The acrylate resin according to the present application contains unsaturated double bonds (such as carbon-carbon double bonds, etc.) at the end of the molecular chain, which can be cross-linked and polymerized under UV light irradiation. The acrylate resin accounts for a high proportion in the entire coating system and constitutes the basic framework of the light-cured coating. In some embodiments, the mass fraction of the acrylate resin in the raw material composition of the self-cleaning wear-resistant UV light curing coating is not less than 30%, and further can be 30% to 70%. The acrylate resin plays a very important role in determining the comprehensive performance (gloss, hardness, flexibility, adhesion, weather resistance, etc.) of the coating.

[0087] The number average molecular weight of the acrylate resin can be 500 to 5000 g / mol, further can be 1000 to 3000 g / mol, and more further can be 1000 to 2000 g / mol.

[0088] The acrylic ester resin can include at least one of epoxy acrylate, polyurethane acrylate, polyether acrylate, polyester acrylate, and preferably can include polyurethane acrylate.

[0089] The acrylic ester resin can include at least one of epoxy acrylate, polyurethane acrylate, polyether acrylate, polyester acrylate, and preferably can include polyurethane acrylate.

[0090] The active diluent can be a small molecule monomer containing unsaturated bonds (such as carbon-carbon double bonds, etc.), which can not only participate in curing, but also reduce the viscosity of the system and change the rheological properties of the system, and on the other hand, also has a certain influence on the final performance of the coating.

[0091] The active diluent can be an acrylic ester small molecule monomer, and can include at least one of methyl acrylate, ethyl acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, diol di(meth) acrylate, hexanediol di(meth) acrylate, tripropyleneglycol diacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and preferably includes at least one of hydroxyethyl (meth) acrylate, tripropyleneglycol diacrylate, and pentaerythritol triacrylate.

[0092] The photoinitiator can absorb the energy of UV light radiation to produce active ions or free radicals as active centers to initiate the reaction. Too much photoinitiator can cause the coating to degrade and age, and too little photoinitiator can affect the curing rate, crosslinking degree, hardness, etc.

[0093] The photoinitiator can include at least one of benzophenone, benzoin ethyl ether, benzoin dimethyl ether, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxy-cyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, and bis-2,4,6-trimethylbenzoyl phenyl phosphine oxide, and preferably includes 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0094] The solvent can include at least one of ethyl acetate, butyl acetate, acetone, butanone, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, trifluorotoluene, p-trifluorotoluene, hydrofluoroether, ethyl nonafluorobutyl ether, heptyl acetate, and propylene glycol monomethyl ether, and preferably includes at least one of ethyl acetate, butyl acetate, acetone, and butanone.

[0095] The leveling agent can be used to improve the flowability of the coating and improve the flatness of the coating surface, and too little leveling agent can affect the leveling effect, and too much leveling agent can affect the anti-fingerprint effect of the coating surface.

[0096] The leveling agent can include at least one of BYK-306, BYK-307, BYK-333, BYK-354, BYK-377, Levaslip 407, Levaslip 410, Levaslip 411, Levaslip 432, Levaslip 466, and preferably at least one of BYK-307 and Levaslip 410.

[0097] The application further provides a preparation method of the self-cleaning wear-resistant UV light-cured coating, comprising: uniformly mixing acrylate resin, reactive diluent, photoinitiator, solvent, perfluoropolyether modified long fluorine side chain polyurethane acrylate, and leveling agent to obtain the self-cleaning wear-resistant UV light-cured coating.

[0098] In the preparation method of the self-cleaning wear-resistant UV light-cured coating, the uniform mixing can be performed by stirring, and further, the stirring speed can be 500-3000 rpm, for example, 1000 rpm, etc.

[0099] The application further provides application of the self-cleaning wear-resistant UV light-cured coating in preparation of a self-cleaning wear-resistant UV light-cured coating layer.

[0100] As a general inventive concept, the application further provides a self-cleaning wear-resistant UV light-cured coating layer, which is formed by film forming, drying, and curing under ultraviolet light irradiation of the self-cleaning wear-resistant UV light-cured coating.

[0101] The application further provides a preparation method of a self-cleaning wear-resistant UV light-cured coating layer, comprising: film forming, drying, and curing under ultraviolet light irradiation of the self-cleaning wear-resistant UV light-cured coating to obtain the self-cleaning wear-resistant UV light-cured coating layer.

[0102] The film forming mode of the self-cleaning wear-resistant UV light-cured coating can not be particularly limited, and can use the prior art, for example, spraying, coating, dipping, pad dyeing, roller coating, or any combination of the above modes, etc.

[0103] The application object of the self-cleaning wear-resistant UV light-cured coating can not be particularly limited, for example, it can be the surface of common plastics (for example, acrylonitrile-butadiene-styrene copolymer ABS, polycarbonate PC, polyethylene terephthalate PET, composite material PC-ABS of polycarbonate and acrylonitrile-butadiene-styrene copolymer, composite material PC-GF of polycarbonate and glass fiber, etc.), leather, paper, metal, glass, etc.

[0104] The drying condition of the self-cleaning wear-resistant UV light-cured coating after film forming can be:

[0105] The drying temperature can be 70-120℃, further can be 70-90℃.

[0106] The drying time can be 1-10 minutes, for example 5 minutes, etc.

[0107] The conditions of the ultraviolet light irradiation can be:

[0108] The ultraviolet light wavelength can be 260-380nm, for example ultraviolet light with a peak value of 365nm, etc.

[0109] The ultraviolet light irradiation energy can be 100-1500mJ / cm 2 , further can be 300-500mJ / cm 2 .

[0110] The coating layer formed by the self-cleaning wear-resistant UV light curing coating can be a nano coating, a micro coating, etc. In some embodiments, the coating layer thickness formed by the self-cleaning wear-resistant UV light curing coating can be 10-100 microns.

[0111] Compared with the prior art, the present application has the following beneficial effects:

[0112] The fluorine-based antifouling additive (i.e. perfluoropolyether modified long fluorine side chain polyurethane acrylate) in the self-cleaning wear-resistant UV light curing coating participates in crosslinking through a photo-curing reaction, the long fluorine side chain perfluoropolyether is not easy to be consumed, and the wear resistance of the coating is improved. And the synergistic effect of the fluorine-based antifouling additive and the low molecular weight multifunctional acrylate and other components improves the mechanical stability, chemical stability and hydrophobic and oleophobic stability of the coating.

[0113] The perfluoropolyether modified long fluorine side chain polyurethane acrylate gives the UV light curing coating excellent hydrophobic and oleophobic properties, anti-graffiti, anti-fingerprint, smoothness, low refraction and wear resistance, etc., and realizes long-term protection of the coating surface.

[0114] The coating surface formed by the self-cleaning wear-resistant UV light curing coating has a water contact angle of not less than 110° and a n-hexadecane static oil contact angle of not less than 65°, and has good antifouling property, fingerprint wiping property and wear resistance.

[0115] The coating layer formed by the self-cleaning wear-resistant UV light curing coating can be applied in the fields of 3C electronics, printed circuit boards (PCB), aerospace, automobiles, military and industry, etc., to protect the interior of the equipment from being contaminated by moisture, chemicals and corrosive substances, and to easily clean the surface of the equipment, and to prevent water, oil, dirt and fingerprints. BRIEF DESCRIPTION OF DRAWINGS

[0116] Figure 1 A schematic diagram of preparing a hydrophobic coating on the surface of a substrate. DETAILED DESCRIPTION

[0117] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Operating methods not specifically specified in the following embodiments are generally performed under conventional conditions or as recommended by the manufacturer.

[0118] Example 1

[0119] In a four-necked flask equipped with a constant-pressure separatory funnel, thermometer, and stirring device, air is purged through a double-row tube, and nitrogen is backfilled. This process is repeated at least three times. Polytetrahydrofuran ether diol (number-average molecular weight M = 500 g / mol) should be dried in an oven at 80°C for at least 24 hours before use, and the solvent should be dehydrated before use. Weigh 1.11 g of isophorone diisocyanate, 3.5 g of polytetrahydrofuran ether diol, and 0.015 wt% butylated hydroxytoluene (based on a total mass of 100% of isophorone diisocyanate and polytetrahydrofuran ether diol), and 0.04 wt% dibutyltin dilaurate (based on a total mass of 100% of isophorone diisocyanate and polytetrahydrofuran ether diol). Add these to a suitable amount of a mixed solvent of acetone and butyl acetate (mass ratio 1:2), mix and dissolve, and then heat to 45°C under a nitrogen atmosphere to react. The content of -NCO groups was determined using the toluene-di-n-butylamine method.

[0120] K-type perfluoropolyether alcohol (PFPE) based on single-terminated hydroxyl groups Synthesis of perfluoropolyether propane 1,2-diol (number average molecular weight M = 500 g / mol) That is, R in compound (IV) a for R b (Methylene), when the -NCO group content determined above reaches the theoretical content, weigh 0.5g of perfluoropolyether propane 1,2-diol and dissolve it in an appropriate amount of p-difluorotoluene. Slowly add it dropwise to the flask through a constant pressure separatory funnel. After the addition is completed, slowly raise the temperature to 80℃ within half an hour and continue stirring. Determine the content of -NCO group using the toluene-di-n-butylamine method.

[0121] When the -NCO group reaches the theoretical content again, the temperature is lowered to 45℃. 0.3g of pentaerythritol triacrylate is weighed and dissolved in an appropriate amount of acetone and butyl acetate mixed solvent. The solution is slowly added dropwise to the flask through a constant pressure separatory funnel. The temperature is raised to 80℃ and stirring is continued. The reaction of the -NCO group is observed by infrared spectroscopy until the reaction is complete.

[0122] The obtained product was washed successively with ethanol and diethyl ether to remove unreacted raw materials, and then dried under vacuum at 60–150 °C for 6–24 hours to obtain a multifunctional fluorinated polymer FUA1 with perfluorinated polyether side groups, with a yield of about 89%.

[0123] Preparation of UV-cured coating: 65.8 parts by mass of polyurethane acrylate with functionality of 3 (number average molecular weight M = 2000 g / mol), 20 parts by mass of reactive diluent tripropyleneglycol diacrylate, 5 parts by mass of solvent ethyl acetate, 5 parts by mass of solvent butyl acetate, 2 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2 parts by mass of FUA1, 0.2 parts by mass of leveling agent BYK-307 were mixed uniformly, and a film was formed on the surface of polycarbonate (PC) by spraying, dried in an oven at 70°C for 5 minutes, irradiated with ultraviolet light with a peak wavelength of 365 nm, and the irradiation energy was 300 mJ / cm 2 The results of the coating performance test are shown in Table 2.

[0124] Example 2

[0125] A four-necked flask equipped with a constant pressure dropping funnel, a thermometer, and a stirring device was evacuated through a double-tube air exhaust, backfilled with nitrogen, and operated at least three times. The polytetramethylene ether glycol (number average molecular weight M = 1000 g / mol) was dried in an oven at 80°C for more than 24 hours before use, and the solvent was dehydrated before use. 1.39 g of toluene diisocyanate, 5.2 g of polytetramethylene ether glycol, 0.012 wt% of 2,6-di-tert-butyl-p-cresol (based on 100% of the total mass of toluene diisocyanate and polytetramethylene ether glycol), and 0.06 wt% of azobisisobutyronitrile (based on 100% of the total mass of toluene diisocyanate and polytetramethylene ether glycol) were added to a suitable amount of a mixed solvent of ethyl acetate and butyl acetate (mass ratio 1:1), mixed and dissolved, and then heated to 50°C for reaction under a nitrogen atmosphere. The content of -NCO groups was calibrated by the toluene-di-n-butylamine method.

[0126] The K-type perfluoropolyether alcohol based on a single terminal hydroxyl group (same as in Example 1, number average molecular weight M = 1000 g / mol) was used to synthesize perfluoropolyether propane 1,2-diol (same as in Example 1). When the -NCO group content determined above reached the theoretical content, 2.0 g of perfluoropolyether propane 1,2-diol was dissolved in a suitable amount of p-perfluorobutyl methyl ether, slowly added to the flask through a constant pressure dropping funnel, and slowly warmed to 75°C within half an hour. The stirring was continued, and the content of -NCO groups was calibrated by the toluene-di-n-butylamine method.

[0127] When the -NCO group content again reached the theoretical content, the temperature was lowered to 50°C, 0.21 g of hydroxyethyl methacrylate was dissolved in a suitable amount of a mixed solvent of ethyl acetate and butyl acetate, slowly added to the flask through a constant pressure dropping funnel, and the temperature was raised to 80°C. The stirring was continued, and the reaction was observed by infrared spectroscopy to determine whether the -NCO group was completely reacted or not until the reaction was complete.

[0128] The obtained product is washed with ethanol and ether in turn, to remove unreacted raw materials, and then vacuum dried at 60-150°C for 6-24 hours to obtain the multifunctional fluorinated polymer FUA2 with side groups of perfluoropolyether, with a yield of about 91%.

[0129] Preparation of the UV-cured coating: 50 parts by mass of epoxy acrylate with a functionality of 3 (number average molecular weight M = 1000 g / mol), 20 parts by mass of methyl acrylate, 13 parts by mass of acetone, 13 parts by mass of butyl acetate, 1.8 parts by mass of benzophenone, 2 parts by mass of FUA2, and 0.2 parts by mass of BYK-333 are uniformly mixed, a film is formed on the surface of polycarbonate (PC) by spraying, dried in an oven at 80°C for 10 minutes, irradiated with ultraviolet light with a peak wavelength of 365 nm, and the irradiation energy is 400 mJ / cm2, and cured into a coating with a thickness of 25 μm. The test results of the coating performance are shown in Table 2. 2 , and cured into a coating with a thickness of 25 μm. The test results of the coating performance are shown in Table 2.

[0130] Example 3

[0131] A four-necked flask is installed with a constant pressure separatory funnel, a thermometer, and a stirring device, and is connected to a double-tube air exhaust and backfilled with nitrogen, which is operated at least three times. The polytetrahydrofuran ether glycol (number average molecular weight M = 2000 g / mol) is dried in an oven at 80°C for more than 24 hours before use, and the solvent is dehydrated before use. 1.25 g of diphenylmethane diisocyanate, 7.5 g of polytetrahydrofuran ether glycol, 0.01 wt% of triphenyl phosphate (based on 100% of the total mass of diphenylmethane diisocyanate and polytetrahydrofuran ether glycol), and 0.05 wt% of t-butyl peroxide (based on 100% of the total mass of diphenylmethane diisocyanate and polytetrahydrofuran ether glycol) are added to a suitable amount of a mixed solvent of acetone and butanone (mass ratio 1:1), mixed and dissolved, and then heated to 50°C for reaction under a nitrogen atmosphere. The content of -NCO groups is calibrated by the toluene-di-n-butylamine method.

[0132] The perfluoropolyether propane 1,2-diol (same as in Example 1) is synthesized based on the single-end hydroxyl group K-type perfluoropolyether alcohol (same as in Example 1, number average molecular weight M = 2000 g / mol). When the -NCO group content determined above reaches the theoretical content, 1.5 g of perfluoropolyether propane 1,2-diol is dissolved in a suitable amount of perfluorobutyl ether, slowly added to the flask through the constant pressure separatory funnel, and slowly heated to 90°C within half an hour after the addition is completed, and continues to be stirred. The content of -NCO groups is calibrated by the toluene-di-n-butylamine method.

[0133] When the -NCO group reaches the theoretical content again, the temperature is lowered to 50°C, 0.15 g of hydroxypropyl methacrylate is weighed into a suitable amount of mixed solvent of acetone and butanone, and slowly added into the flask through a constant pressure separatory funnel. The temperature is raised to 90°C, and the stirring is continued. The reaction is observed by infrared spectroscopy until the -NCO group is completely reacted.

[0134] The obtained product is washed with ethanol and diethyl ether in turn to remove the unreacted raw materials, and then vacuum dried at 60-150°C for 6-24 hours to obtain the multifunctional fluorinated polymer FUA3 with side groups of perfluoropolyether, with a yield of about 90%.

[0135] Preparation of the UV-cured coating: 55 parts by mass of polyester acrylate with a functionality of 3 (number average molecular weight M = 1500 g / mol), 25 parts by mass of ethyl acrylate, 8.4 parts by mass of ethyl acetate, 8.4 parts by mass of butyl acetate, 2 parts by mass of benzoin ethyl ether, 1 part by mass of FUA3, and 0.2 parts by mass of BYK-306 are uniformly mixed, and a film is formed on the surface of acrylonitrile-butadiene-styrene copolymer (ABS) by spraying. The film is dried in an oven at 75°C for 8 minutes, irradiated with ultraviolet light with a peak wavelength of 365 nm, and the irradiation energy is 500 mJ / cm 2 , to form a coating with a thickness of 20 μm. The test results of the coating performance are shown in Table 2.

[0136] Example 4

[0137] A four-necked flask equipped with a constant pressure separatory funnel, a thermometer, and a stirring device is installed with a double-tube air exhaust and backfilled with nitrogen, and the operation is performed at least three times. Polycarbonate diol (number average molecular weight M = 1000 g / mol) is dried in an oven at 80°C for more than 24 hours before use, and the solvent is water-free before use. 1.32 g of dicyclohexylmethane diisocyanate, 3.5 g of polycarbonate diol, 0.015 wt% of sulfurized isobutyl phenol (based on 100% of the total mass of dicyclohexylmethane diisocyanate and polycarbonate diol), and 0.04 wt% of dibutyltin dilaurate (based on 100% of the total mass of dicyclohexylmethane diisocyanate and polycarbonate diol) are weighed into a suitable amount of mixed solvent of butanone and butyl acetate (mass ratio 1:2), mixed and dissolved, and then heated to 55°C under a nitrogen atmosphere for reaction. The content of -NCO group is calibrated by the toluene-dinormal butylamine method.

[0138] Synthesis of perfluoropolyether propane 1,2-diol (same as Example 1) based on single end hydroxyl group K type perfluoropolyether alcohol (same as Example 1, number average molecular weight M = 3000 g / mol), when the -NCO group reaches the theoretical content by the above-mentioned method, weigh 3 g of perfluoropolyether propane 1,2-diol dissolved in an appropriate amount of trifluorotoluene, slowly drop into the flask through the constant pressure burette, slowly warm up to 85°C within half an hour after the drop is completed, continue to stir, and calibrate the content of -NCO group by toluene-dibutylamine method.

[0139] When the -NCO group reaches the theoretical content again, cool down to 55°C, weigh 0.12 g of hydroxyethyl acrylate dissolved in an appropriate amount of butanone and butyl acetate mixed solvent, slowly drop into the flask through the constant pressure burette, warm up to 85°C, continue to stir, and observe whether the -NCO group is completely reacted by infrared spectroscopy until the reaction is complete.

[0140] The resulting product is washed with ethanol and diethyl ether in turn to remove unreacted raw materials, and then vacuum dried at 60-150°C for 6-24 hours to obtain a multifunctional fluorinated polymer FUA4 with side groups of perfluoropolyether, with a yield of about 92%.

[0141] Preparation of ultraviolet light cured coating: 45 parts by mass of polyether acrylate with a functionality of 3 (number average molecular weight M = 2000 g / mol), 30 parts by mass of hydroxyethyl methacrylate, 6 parts by mass of butanone, 16.8 parts by mass of butyl acetate, 1.5 parts by mass of benzoin dimethyl ether, 0.5 parts by mass of FUA4, and 0.2 parts by mass of BYK-354 are mixed uniformly, a film is formed on the surface of polyethylene terephthalate (PET) by spraying, dried in an oven at 85°C for 10 minutes, irradiated with ultraviolet light with a peak wavelength of 365 nm, the irradiation energy is 600 mJ / cm 2 , and cured into a 15 μm thick coating. The test results of the coating performance are shown in Table 2.

[0142] Example 5

[0143] A four-necked flask equipped with a constant pressure dropping funnel, a thermometer, and a stirring device was evacuated through a double-tube air vent and backfilled with nitrogen at least three times. The polycarbonate diol (number average molecular weight M = 2000 g / mol) was dried in an oven at 80°C for 24 hours or more before use, and the solvent was dehydrated before use. 1.53 g of hexamethylene diisocyanate, 4.08 g of polycarbonate diol, 0.015 wt% of butylated hydroxytoluene (based on the total mass of hexamethylene diisocyanate and polycarbonate diol, 100%), and 0.04 wt% of azobisisobutyronitrile (based on the total mass of hexamethylene diisocyanate and polycarbonate diol, 100%) were added to a suitable amount of a mixed solvent of methyl ethyl ketone and ethyl acetate (mass ratio 1:2), mixed and dissolved, and then heated to 50°C under a nitrogen atmosphere to react. The content of -NCO groups was calibrated using the toluene-di-n-butylamine method.

[0144] A perfluoropolyether alcohol of K type based on a single terminal hydroxyl group (same as in Example 1, number average molecular weight M = 4000 g / mol) was used to synthesize a perfluoropolyether propane 1,2-diol (same as in Example 1). When the -NCO group content determined as described above reached the theoretical content, 3.5 g of the perfluoropolyether propane 1,2-diol was dissolved in a suitable amount of p-hydrofluoroether, slowly added to the flask through a constant pressure dropping funnel, and slowly warmed to 80°C within half an hour. Stirring was continued, and the content of -NCO groups was calibrated using the toluene-di-n-butylamine method.

[0145] When the -NCO group content again reached the theoretical content, the temperature was lowered to 50°C, 0.14 g of hydroxypropyl acrylate was dissolved in a suitable amount of a mixed solvent of methyl ethyl ketone and ethyl acetate, slowly added to the flask through a constant pressure dropping funnel, and warmed to 80°C. Stirring was continued, and the reaction of -NCO groups was observed by infrared spectroscopy until completion.

[0146] The resulting product was washed with ethanol and diethyl ether in sequence to remove unreacted raw materials, and then dried under vacuum at 60-150°C for 6-24 hours to obtain a multifunctional fluorinated polymer FUA5 having a perfluoropolyether side group, with a yield of about 91%.

[0147] Preparation of an ultraviolet light-cured coating: 60 parts by mass of a polyurethane acrylate having a functionality of 9 (number average molecular weight M = 1800 g / mol), 20 parts by mass of hydroxypropyl methacrylate, 10 parts by mass of ethyl acetate, 7.8 parts by mass of acetone, 1.8 parts by mass of 1-hydroxy-cyclohexyl phenyl ketone, 0.2 parts by mass of FUA5, and 0.2 parts by mass of BYK-377 were mixed uniformly, and a film was formed on the surface of a polycarbonate and acrylonitrile-butadiene-styrene copolymer composite material PC-ABS by spraying. The film was dried in an oven at 80°C for 8 minutes, irradiated with ultraviolet light having a peak wavelength of 365 nm at an energy of 700 mJ / cm 2 , and cured to a thickness of 20 μm. The results of the coating performance tests are shown in Table 2.

[0148] Example 6

[0149] A four-necked flask equipped with a constant pressure dropping funnel, a thermometer, a stirring device, and a double-tube air exhaust and nitrogen backfilling device was operated at least three times. A hydroxyl-terminated perfluoropolyether alcohol D2 (Solvay, Italy, number average molecular weight M = 1500 g / mol) was dried in an oven at 80°C for more than 24 hours before use, and the solvent was dehydrated before use. 0.93 g of isophorone diisocyanate, 2.5 g of a hydroxyl-terminated perfluoropolyether alcohol D2, 0.015 wt% of 2,6-di-tert-butyl-p-cresol (based on the total mass of isophorone diisocyanate and D2, 0.04 wt% of tert-butyl peroxide (based on the total mass of isophorone diisocyanate and D2), was added to a mixed solvent of ethyl acetate and butyl acetate (mass ratio 1:1), mixed and dissolved, and then heated to 55°C under a nitrogen atmosphere for reaction. The content of -NCO groups was determined by the toluene-di-n-butylamine method.

[0150] A perfluoropolyether propane 1,2-diol was synthesized based on a hydroxyl-terminated K-type perfluoropolyether alcohol (as in Example 1, number average molecular weight M = 2000 g / mol). When the -NCO group content determined above reached the theoretical content, 2.5 g of the perfluoropolyether propane 1,2-diol was dissolved in an appropriate amount of ethyl nonafluorobutyl ether, slowly added to the flask through a constant pressure dropping funnel, and slowly warmed to 90°C within half an hour. Stirring was continued, and the content of -NCO groups was determined by the toluene-di-n-butylamine method.

[0151] When the -NCO group content again reached the theoretical content, the temperature was lowered to 55°C, 0.25 g of pentaerythritol triacrylate was dissolved in an appropriate amount of a mixed solvent of ethyl acetate and butyl acetate, slowly added to the flask through a constant pressure dropping funnel, and warmed to 90°C. Stirring was continued, and the reaction of -NCO groups was observed by infrared spectroscopy until completion.

[0152] The resulting product was washed with ethanol and diethyl ether in sequence to remove unreacted raw materials, and then vacuum dried at 60-150°C for 6-24 hours to obtain a multifunctional fluorinated polymer FUA6 having a perfluoropolyether side group, with a yield of about 88%.

[0153] Preparation of UV-cured coating: 30 parts by mass of polyurethane acrylate with functionality of 3 (number average molecular weight M = 2000 g / mol) and 30 parts by mass of epoxy acrylate with functionality of 3 (number average molecular weight M = 1000 g / mol), 20 parts by mass of hexanediol diacrylate, 9 parts by mass of ethyl acetate, 8.8 parts by mass of butyl acetate, 1.7 parts by mass of 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 0.3 parts by mass of FUA6, 0.2 parts by mass of BYK-377 were uniformly mixed, and a film was formed on the surface of PC by spraying, dried in an oven at 80°C for 10 minutes, irradiated with ultraviolet light with a peak wavelength of 365 nm, and the irradiation energy was 800 mJ / cm 2 , to form a 25 μm thick coating. The results of the coating performance test are shown in Table 2.

[0154] Example 7

[0155] A four-necked flask equipped with a constant pressure dropping funnel, a thermometer, and a stirring device was installed, and air was discharged through a double-tube air pipe and replaced with nitrogen at least three times. Polytetrahydrofuran ether glycol (number average molecular weight M = 1000 g / mol) was dried in an oven at 80°C for more than 24 hours before use, and the solvent was dehydrated before use. 0.37 g of 1,4-cyclohexane diisocyanate, 1.43 g of polytetrahydrofuran ether glycol, 0.015 wt% of triphenyl phosphate (based on 100% of the total mass of 1,4-cyclohexane diisocyanate and polytetrahydrofuran ether glycol), and 0.04 wt% of dibutyltin dilaurate (based on 100% of the total mass of 1,4-cyclohexane diisocyanate and polytetrahydrofuran ether glycol) were weighed and added to a mixed solvent of acetone and butyl acetate (mass ratio of 1:2), and then dissolved by mixing, and then heated to 50°C under a nitrogen atmosphere. The content of -NCO groups was calibrated by the toluene-di-n-butylamine method.

[0156] Synthesis of perfluoropolyether propane 1,2-diol based on Z-type perfluoropolyether alcohol with a single terminal hydroxyl group (number average molecular weight M = 4000 g / mol) When the -NCO group content reached the theoretical value in the above determination, 2.2 g of perfluoropolyether propane 1,2-diol was dissolved in a suitable amount of p-ditolyl trifluoromethylbenzene, and was slowly added to the flask through a constant pressure dropping funnel. The temperature was slowly raised to 85°C within half an hour after the addition was completed, and the stirring was continued. The content of -NCO groups was calibrated by the toluene-di-n-butylamine method.

[0157] When the -NCO group content reached the theoretical value again, the temperature was lowered to 50°C, 0.14 g of pentaerythritol triacrylate was dissolved in a suitable amount of a mixed solvent of acetone and butyl acetate, and was slowly added to the flask through a constant pressure dropping funnel. The temperature was raised to 85°C, and the stirring was continued. Whether the -NCO group was completely reacted or not was observed by infrared spectroscopy until the reaction was complete.

[0158] The resulting product was washed with ethanol and diethyl ether in turn to remove unreacted starting materials, and then vacuum dried at 60-150 °C for 6-24 hours to obtain the multi-functionality fluorinated polymer FUA7 with side groups of perfluoropolyether, with a yield of about 90%.

[0159] Preparation of UV-cured coating: 25 parts by mass of polyurethane acrylate with functionality of 9 (number average molecular weight M = 2000 g / mol) and 25 parts by mass of polyester acrylate with functionality of 3 (number average molecular weight M = 2000 g / mol), 20 parts by mass of tripropyleneglycol diacrylate, 13 parts by mass of ethyl acetate, 13 parts by mass of butanone, 1.5 parts by mass of bis-2,4,6-trimethylbenzoylphenylphosphine oxide, 0.5 parts by mass of FUA7, 0.2 parts by mass of Levaslip 407 were mixed uniformly, and a film was formed on the surface of PC by spraying, dried in an oven at 90 °C for 8 minutes, and irradiated with UV light with a peak wavelength of 365 nm at an energy of 1000 mJ / cm2to cure into a coating layer with a thickness of 25 μm. The results of the coating layer performance test are shown in Table 2. 2

[0160] Example 8

[0161] A four-necked flask equipped with a constant pressure dropping funnel, a thermometer, and a stirring device was evacuated through a double-tube air exhaust, and backfilled with nitrogen, at least three times. Polycarbonate diol (number average molecular weight M = 1000 g / mol) was dried in an oven at 80 °C for more than 24 hours before use, and the solvent was dehydrated before use. 1.21 g of isophorone diisocyanate, 3.71 g of polytetrahydrofuran ether diol, 0.015 wt% of sulfurized isobutyl phenol (based on 100% of the total mass of isophorone diisocyanate and polycarbonate diol), and 0.04 wt% of azobisisobutyronitrile (based on 100% of the total mass of isophorone diisocyanate and polycarbonate diol) were added to a suitable amount of a mixed solvent of acetone and butyl acetate (mass ratio of 1:2), mixed and dissolved, and then heated to 45 °C for reaction under a nitrogen atmosphere. The content of -NCO groups was calibrated by the toluene-di-n-butylamine method.

[0162] Synthesis of perfluoropolyether alcohol Y-type with a single terminal hydroxyl group Synthesis of perfluoropolyether propane 1,2-diol by ring-opening of perfluoropolyether alcohol Y-type with a single terminal hydroxyl group When the -NCO group content determined above reached the theoretical content, 2.4 g of perfluoropolyether propane 1,2-diol was dissolved in a suitable amount of perfluorobutyl ethyl ether, and slowly added dropwise to the flask through a constant pressure dropping funnel. After the addition was completed, the temperature was slowly increased to 80 °C within half an hour, and the stirring was continued. The content of -NCO groups was calibrated by the toluene-di-n-butylamine method.

[0163] ​When the -NCO group reaches the theoretical content again, the temperature is lowered to 45°C, 0.16 g of 4-hydroxybutyl acrylate is weighed into a suitable amount of a mixed solvent of acetone and butyl acetate, and slowly added dropwise into the flask through a constant pressure separatory funnel, the temperature is raised to 80°C, and stirring is continued. The reaction is complete when the -NCO group is completely reacted, as observed by infrared spectroscopy.

[0164] The resulting product is washed with ethanol and diethyl ether in turn to remove unreacted raw materials, and then vacuum dried at 60-150°C for 6-24 hours to obtain the multifunctional fluorinated polymer FUA8 with side groups of perfluoropolyether, with a yield of about 90%.

[0165] Preparation of an ultraviolet light-cured coating: 25 parts by mass of epoxy acrylate (number average molecular weight M = 1000 g / mol) and 30 parts by mass of polyether acrylate (number average molecular weight M = 1500 g / mol), 25 parts by mass of tripropyleneglycol diacrylate, 8.8 parts by mass of ethyl acetate, 8 parts by mass of butyl acetate, 0.5 parts by mass of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1.5 parts by mass of FUA1, and 0.2 parts by mass of BYK-307 are mixed uniformly, a film is formed on the surface of PC by spraying, dried in an oven at 70°C for 5 minutes, irradiated with ultraviolet light with a peak wavelength of 365 nm, and the irradiation energy is 900 mJ / cm 2 , to form a 5 μm thick coating. The results of the coating performance tests are shown in Table 2.

[0166] Example 9

[0167] A four-necked flask equipped with a constant pressure separatory funnel, a thermometer, and a stirring device is installed with a double-tube air exhaust and backfilled with nitrogen, and the operation is performed at least three times. Polycarbonate diol (number average molecular weight M = 1000 g / mol) is dried in an oven at 80°C for more than 24 hours before use, and the solvent is dehydrated before use. 0.68 g of hexamethylene diisocyanate, 2.58 g of polytetrahydrofuran ether diol, 0.015 wt% of butylated hydroxytoluene (based on 100% of the total mass of hexamethylene diisocyanate and polytetrahydrofuran ether diol), and 0.04 wt% of t-butyl peroxide (based on 100% of the total mass of hexamethylene diisocyanate and polytetrahydrofuran ether diol) are weighed into a suitable amount of a mixed solvent of methyl ethyl ketone and butyl acetate (mass ratio 1:2), mixed and dissolved, and then heated to 55°C under a nitrogen atmosphere for reaction. The content of -NCO groups is calibrated by the toluene-di-n-butylamine method.

[0168] Synthesis of perfluoropolyether propane 1,2-diol based on the ring-opening of D-type perfluoropolyether alcohol with a single terminal hydroxyl group (number average molecular weight M = 2000 g / mol) When the -NCO group reaches the theoretical content in the above determination, 2.1 g of perfluoropolyether propane 1,2-diol is weighed into the appropriate amount of trifluorotoluene, slowly added to the flask through the constant pressure separatory funnel, and slowly warmed to 95°C within half an hour after the addition is complete. Continue to stir and calibrate the -NCO group content with the toluene-dibutylamine method.

[0169] When the -NCO group reaches the theoretical content again, cool to 55°C, weigh 0.24 g of pentaerythritol triacrylate into the appropriate amount of butanone and butyl acetate mixed solvent, slowly add to the flask through the constant pressure separatory funnel, warm to 95°C, continue to stir, and observe whether the -NCO group is completely reacted by infrared spectroscopy until the reaction is complete. The resulting product is washed with ethanol and diethyl ether in turn to remove unreacted raw materials, and then vacuum dried at 60-150°C for 6-24 hours to obtain a multifunctional fluorinated polymer FUA9 with perfluoropolyether side groups, with a yield of about 90%.

[0170] Preparation of an ultraviolet light-cured coating: 35 parts by mass of a polyurethane acrylate with a functionality of 3 (number average molecular weight M = 2000 g / mol) and 30 parts by mass of a polyether acrylate with a functionality of 3 (number average molecular weight M = 1000 g / mol), 15 parts by mass of trimethylolpropane triacrylate, 9 parts by mass of ethyl acetate, 8.8 parts by mass of butyl acetate, 1 part by mass of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1 part by mass of FUA7, and 0.2 parts by mass of Levaslip 411 are mixed uniformly, a film is formed on the surface of an acrylonitrile-butadiene-styrene copolymer (ABS) by spraying, dried in an oven at 70°C for 5 minutes, irradiated with ultraviolet light with a peak wavelength of 365 nm at an irradiation energy of 1200 mJ / cm 2 , and cured into a 10 μm thick coating. The results of the coating performance tests are shown in Table 2.

[0171] Example 10

[0172] A four-necked flask equipped with a constant pressure separatory funnel, a thermometer, and a stirring device is evacuated through a double-tube air vent and backfilled with nitrogen at least three times. The polytetramethylene ether glycol (number average molecular weight M = 1000 g / mol) is dried in an oven at 80°C for 24 hours or more before use, and the solvent is dehydrated before use. 0.58 g of toluene diisocyanate, 2.01 g of polytetramethylene ether glycol, 0.01 wt% of 2,6-di-tert-butyl-p-cresol (based on 100% of the total mass of toluene diisocyanate and polytetramethylene ether glycol), and 0.05 wt% of dibutyltin dilaurate (based on 100% of the total mass of toluene diisocyanate and polytetramethylene ether glycol) are added to the appropriate amount of a mixed solvent of ethyl acetate and butyl acetate (mass ratio 1:1), mixed and dissolved, and then heated to 50°C under a nitrogen atmosphere to react. The -NCO group content is calibrated with the toluene-dibutylamine method.

[0173] Synthesis of perfluoropolyether alcohol Y type based on single end hydroxyl group Synthesis of perfluoropolyether propane 1,2-diol When the -NCO group reaches the theoretical content in the above determination, 2.8 g of perfluoropolyether propane 1,2-diol is weighed into the flask and slowly added through a constant pressure dropping funnel, and slowly heated to 80°C within half an hour after the addition is completed, and stirring is continued, and the content of -NCO group is calibrated by the toluene-dibutylamine method.

[0174] When the -NCO group reaches the theoretical content again, the temperature is lowered to 50°C, 0.09 g of hydroxyethyl methacrylate is dissolved in a mixture of ethyl acetate and butyl acetate, and slowly added through a constant pressure dropping funnel, and heated to 80°C, and stirring is continued, and whether the -NCO group is completely reacted is observed by infrared spectroscopy until the reaction is complete.

[0175] The obtained product is washed with ethanol and diethyl ether in turn to remove unreacted raw materials, and then vacuum dried at 60-150°C for 6-24 hours to obtain a multifunctional fluorinated polymer FUA10 with a side group of perfluoropolyether, with a yield of about 90%.

[0176] Preparation of ultraviolet light cured coating: 30 parts by mass of epoxy acrylate (number average molecular weight M = 1500 g / mol) and 35 parts by mass of polyester acrylate (number average molecular weight M = 1500 g / mol), 15 parts by mass of pentaerythritol triacrylate, 8.8 parts by mass of acetone, 9 parts by mass of butyl acetate, 1.2 parts by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 0.8 parts by mass of FUA10, and 0.2 parts by mass of Levaslip 432 are mixed uniformly, and a film is formed on the surface of a polycarbonate and glass fiber composite material (PC-GF) by spraying, dried in an oven at 100°C for 5 minutes, irradiated with ultraviolet light with a peak wavelength of 365 nm, and the irradiation energy is 1500 mJ / cm 2 , and cured into a coating layer with a thickness of 15 μm. The test results of the coating layer performance are shown in Table 2.

[0177] Comparative Example 1

[0178] Preparation of ultraviolet light cured coating: 65.8 parts by mass of polyurethane acrylate with a functionality of 3 (number average molecular weight M = 2000 g / mol), 20 parts by mass of tripropyleneglycol diacrylate, 5 parts by mass of ethyl acetate, 5 parts by mass of butyl acetate, 2 parts by mass of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 0.2 parts by mass of BYK-307 are mixed uniformly, and a film is formed on the surface of PC by spraying, dried in an oven at 70°C for 5 minutes, irradiated with ultraviolet light with a peak wavelength of 365 nm, and the irradiation energy is 300 mJ / cm2 The coating was cured into a 25 μm thick coating. The coating performance test results are shown in Table 2.

[0179] Comparative Example 2

[0180] A four-necked flask equipped with a constant pressure dropping funnel, a thermometer, a stirring device, and through which air was exhausted and replaced by nitrogen at least three times. The polytetramethylene ether glycol (number average molecular weight M = 1000 g / mol) was dried in an oven at 80°C for more than 24 hours before use, and the solvent was dehydrated before use. 0.93 g of isophorone diisocyanate, 3.54 g of polytetramethylene ether glycol, 0.015 wt% of butylated hydroxytoluene (based on 100% of the total mass of isophorone diisocyanate and polytetramethylene ether glycol), and 0.04 wt% of dibutyltin dilaurate (based on 100% of the total mass of isophorone diisocyanate and polytetramethylene ether glycol) were weighed into a suitable amount of a mixed solvent of acetone and butyl acetate (mass ratio 1:2), mixed and dissolved, and then heated to 45°C under a nitrogen atmosphere for reaction. The content of -NCO groups was calibrated by the toluene-di-n-butylamine method.

[0181] When the -NCO groups reached the theoretical content in the above determination, 13 mg of ethylene glycol was weighed and slowly added to the flask through the constant pressure dropping funnel. After the addition was completed, the temperature was slowly raised to 80°C within half an hour, and the stirring was continued. The content of -NCO groups was calibrated by the toluene-di-n-butylamine method.

[0182] When the -NCO groups again reached the theoretical content, the temperature was lowered to 45°C, 0.25 g of pentaerythritol triacrylate was dissolved in a suitable amount of a mixed solvent of acetone and butyl acetate, and slowly added to the flask through the constant pressure dropping funnel. The temperature was raised to 80°C, and the stirring was continued. Whether the -NCO groups were completely reacted or not was observed by infrared spectroscopy until the reaction was complete.

[0183] The resulting product was washed with ethanol and diethyl ether in turn to remove unreacted raw materials, and then vacuum dried at 60-150°C for 6-24 hours to obtain a hydrogenated polyurethane acrylate PUA with a yield of about 92%.

[0184] Preparation of an ultraviolet light-cured coating: 65.8 parts by mass of a polyurethane acrylate with a functionality of 3 (number average molecular weight M = 2000 g / mol), 20 parts by mass of tripropyleneglycol diacrylate, 5 parts by mass of ethyl acetate, 5 parts by mass of butyl acetate, 2 parts by mass of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2 parts by mass of PUA, and 0.2 parts by mass of BYK-307 were uniformly mixed, and a film was formed on the surface of PC by spraying. The film was dried in an oven at 70°C for 5 minutes, and then irradiated with ultraviolet light with a peak wavelength of 365 nm at an energy of 300 mJ / cm 2 The coating was cured into a 25 μm thick coating. The coating performance test results are shown in Table 2.

[0185] Characterization was performed on perfluoropolyether-modified polyurethane acrylate (FUA) with long fluorinated side chains. (H NMR spectroscopy) 1 The 1H NMR spectrum, which originally showed the peak of H atomization at the -OH group in the PFPE molecule, has disappeared, indicating that the terminal hydroxyl group has completely reacted. Simultaneously, the fluorine NMR spectrum of FUA... 19 F NMR spectroscopy confirmed the successful presence of PFPE in the FUA molecular chain structure. The infrared spectrum of FUA confirmed the complete reaction of -NCO and -OH and the introduction of F into FUA. The differential scanning calorimetry (DSC) curve of FUA showed neither melting nor crystallization peaks, indicating the absence of large-grained macroscopic crystalline regions in FUA. The FUA molecular chain segments exhibited good compatibility. Thermogravimetric (TG) curves showed that PUA began to decompose below 300℃, while FUA remained stable at 280℃. Therefore, from a structural perspective, FUA with introduced perfluoropolyether branched structures generally exhibited higher thermal oxidation stability. When FUA was dissolved in N,N-dimethylformamide (DMF), cast into films, and the solvent was removed, the water contact angles were 115° for FUA1, 117° for FUA2, 117° for FUA3, 119° for FUA4, and 116° for FUA5. The contact angle of hexadecane for FUA1 is 74°, for FUA2 it is 77°, for FUA3 it is 81°, for FUA4 it is 83°, and for FUA5 it is 78°. The molecular weights of FUA1 to FUA10 are shown in Table 1. The values ​​represent the number-average molecular weight. Furthermore, the actual fluorine content of the FUA was determined by oxygen flask combustion-thorium nitrate titration, and the results are shown in Table 1. The prepared FUA exhibits a high fluorine content.

[0186] Table 1

[0187]

[0188] Table 2 shows the results of water contact angle, oil contact angle, adhesion, oil pen wiping and fingerprint resistance of the coatings prepared in each embodiment and comparative example.

[0189] Table 2

[0190]

[0191] The results in Table 2 show that the coating surface prepared using the perfluoropolyether-modified long-fluorinated side-chain polyurethane acrylate of the present invention has a water contact angle of not less than 110° and an oil (n-hexadecane) contact angle of not less than 65°. Compared with Comparative Examples 1 and 2, the coating prepared using the perfluoropolyether-modified long-fluorinated side-chain polyurethane acrylate of the present invention has higher water and oil contact angles. Furthermore, after 1000 cycles of steel wool rubbing, the coating exhibits excellent abrasion resistance and hydrophobic and oleophobic stability. In addition, dark stains are easily removed from the surface of the coating prepared using the perfluoropolyether-modified long-fluorinated side-chain polyurethane acrylate of the present invention. In contrast, when coatings were prepared using a comparative coating (Comparative Example 1) without perfluoropolyether-modified long-fluorinated side-chain polyurethane acrylate and a comparative coating (Comparative Example 2) using hydrogenated polyurethane acrylate, stains that could not be eliminated were observed. Similar results were observed in the fingerprint easy-to-clean test. Therefore, the coating prepared by the present invention has excellent hydrophobic, oleophobic, anti-fouling, anti-fingerprint, and abrasion-resistant properties.

[0192] This invention relates to some performance testing methods:

[0193] (1) Molecular weight (GPC)

[0194] The average molecular weight and its distribution were determined using a Waters Wyatt WH2-05 GPC instrument. N,N-dimethylformamide was used as the mobile phase at a flow rate of 1.0 mL / min. The molecular weight was corrected using polystyrene standards.

[0195] (2) Actual fluorine content

[0196] The fluoride content was determined by oxygen flask combustion-thorium nitrate titration method, according to the method in the Chinese Pharmacopoeia.

[0197] (3) Nuclear magnetic fluorine spectrum

[0198] 1H NMR (1H NMR) 1 H NMR) and nuclear magnetic fluorine spectroscopy (NMR) 19 F NMR was measured at 25°C using a nuclear magnetic resonance spectrometer (Bruker, Germany, 600MHz).

[0199] (4) Infrared spectroscopy (FT-IR)

[0200] Fourier transform infrared (FT-IR) spectral analysis of the samples was performed using an infrared spectrometer (Thermo Fisher Scientific, iS50 model), with a frequency range of 4000-400 cm⁻¹. -1 .

[0201] (5) Differential Scanning Calorimetry (DSC)

[0202] Thermodynamic measurements were performed on samples using a differential scanning calorimeter (Mettler-Toledo, DSC3 model) in the temperature range -50 to 200 °C at a rate of 10 °C / min under a nitrogen flow of 50 mL / min.

[0203] (6) Thermogravimetric analysis (TG)

[0204] Thermal stability tests were performed using a thermogravimetric analyzer (Mettler-Toledo, TGA2 model) in a nitrogen atmosphere (50 mL / min) from 25 °C to 600 °C at a rate of 20 °C / min.

[0205] (7) Water contact angle

[0206] Characterized by a video optical contact angle meter (Dataphysics, OCA20 model) at 25 °C using 5 μL water droplets. Each reported water contact angle data represents the average of at least five measurements.

[0207] (8) Oil contact angle

[0208] Characterized by a video optical contact angle meter (Dataphysics, OCA20 model) at 25 °C using 3 μL of n-hexadecane. Each reported water contact angle data represents the average of at least five measurements.

[0209] (9) Adhesion

[0210] Determined by the crosshatch method according to GB / T 9286-1998 or ASTM D3359 method.

[0211] (10) Rub-off resistance test

[0212] Tested according to RIM WI-QMR-06-002 standard test using a SDR339-A abrasion tester (Shenzhen SDR Technology Co., Ltd.) with a load of 1000 g, 0000# steel wool reciprocating friction for 1000 times, cycle speed of 60 times / min, and friction length of 5 cm.

[0213] (11) Oil-based pen rub-off

[0214] The surface state of the coating after 3 times of wiping with Kimwipes after drawing lines on the coating surface using Zebra's marker pen and the repulsion of the oil-based ink and the oil-based ink attached after 1 minute of standing was determined by visual method.

[0215] In this oil-based pen rub-off test:

[0216] - indicates smudging

[0217] + indicates halo

[0218] ++ indicates no smudging.

[0219] (12) Anti-fingerprint property

[0220] The anti-fingerprint test was performed according to method MIL-C-15074E using synthetic sebum commercially available from Scientific Services S / D Inc. The synthetic sebum mass composition was as follows:

[0221] Squalene (5%),

[0222] Stearic acid (5%),

[0223] Cholesterol (5%),

[0224] Linoleic acid (5%),

[0225] Paraffin (10%),

[0226] Oleic acid (10%),

[0227] Palmitic acid (10%),

[0228] Coconut oil (15%),

[0229] Synthetic Spermacetti (15%),

[0230] Olive oil (20%).

[0231] In this anti-fingerprint test:

[0232] - indicates smudging

[0233] + indicates halo

[0234] ++ indicates no smudging.

[0235] Furthermore, it is understood that various modifications or changes can be made to the application by those skilled in the art in light of the above teachings without departing from the scope of the application as defined by the appended claims.

Claims

1. A self-cleaning, wear-resistant, UV-curable coating, characterized in that, The raw material composition, by weight parts, includes: The perfluoropolyether-modified long-fluorinated side-chain polyurethane acrylate has the structure shown in formula (I): In formula (I): Both m and n are integers, 1≤m≤30, 1≤n≤24; R1 is selected from the following structure: R2 is selected from structures (a) to (c): (a) Wherein, K is selected from H and F, R' is selected from H and C1-C5 alkyl groups, p is an integer from 1 to 5, and q is an integer from 1 to 200; (b) Wherein, R” is a C2-C6 alkyl group, and a is an integer from 4 to 17; (c) Where b, c, d, and f are each independent integers from 0 to 100, and e is an integer from 3 to 200; R3 conforms to the following formula: GR f -G'- In the formula: G is selected from -F, -CF2Cl, -CF2CF2Cl, -CF2COOM, and non-functional straight-chain or branched C1-C4 perfluoroalkyl groups; M is selected from cationic Na. + K + 、Rb + Cs + ; R f The chemical structure is as follows: Where g, h, i, and j are independent integers from 0 to 300, and the sum of g, h, i, and j is greater than 5; G' is selected from non-functional straight-chain or branched C1-C4 perfluoroalkylene groups; R a It is a C1-C5 saturated chain hydrocarbon group containing an ether bond; R b It is a C1-C5 alkylene group; R4 conforms to the following formula: In the formula, k is an integer from 1 to 3; X is selected from hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, and straight-chain or branched alkyl groups having 1 to 21 carbon atoms; Y is selected from O and NH; Z is selected from chain aliphatic groups with 1 to 21 carbon atoms, aromatic groups with 6 to 10 carbon atoms, and cyclic aliphatic groups with 6 to 10 carbon atoms.

2. The self-cleaning, wear-resistant, UV-curable coating according to claim 1, characterized in that, The raw material composition, by weight parts, includes:

3. The self-cleaning, wear-resistant, UV-curable coating according to claim 1, characterized in that, The acrylate resin molecular chain ends contain unsaturated double bonds, which can be cross-linked and polymerized under UV light irradiation; The raw material composition of the self-cleaning wear-resistant UV curable coating is 100 parts by weight of acrylate resin, reactive diluent, photoinitiator, solvent, perfluoropolyether modified long fluorine side chain polyurethane acrylate and leveling agent. In the raw material composition of the self-cleaning wear-resistant UV-curable coating, the mass percentage of the acrylic resin is not less than 30%. The number-average molecular weight of the acrylate resin is 500–5000 g / mol; The functionality of the acrylate resin is 2 to 9; The acrylate resin is at least one of epoxy acrylate, polyurethane acrylate, polyether acrylate, and polyester acrylate.

4. The self-cleaning, wear-resistant, UV-curable coating according to claim 3, characterized in that, In the raw material composition of the self-cleaning wear-resistant UV-curable coating, the mass percentage of the acrylic resin is 30% to 70%. The number average molecular weight of the acrylate resin is 1000-3000 g / mol.

5. The self-cleaning, wear-resistant, UV-curable coating according to claim 4, characterized in that, The number average molecular weight of the acrylate resin is 1000-2000 g / mol.

6. The self-cleaning, wear-resistant, UV-curable coating according to claim 1, characterized in that, The reactive diluent is an acrylate small molecule monomer, and is at least one of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, diol di(meth)acrylate, tripropylene glycol diacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate.

7. The self-cleaning, wear-resistant, UV-curable coating according to claim 6, characterized in that, The diol di(meth)acrylate is hexanediol di(meth)acrylate.

8. The self-cleaning, wear-resistant, UV-curable coating according to claim 1, characterized in that, The photoinitiator includes at least one of benzophenone, benzoin ether, benzoin dimethyl ether, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxy-cyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and bis2,4,6-trimethylbenzoyl phenylphosphine oxide.

9. The self-cleaning, wear-resistant, UV-curable coating according to claim 1, characterized in that, The solvent is at least one selected from ethyl acetate, butyl acetate, acetone, butanone, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, trifluorotoluene, p-difluorotoluene, hydrofluoroether, ethyl nonafluorobutyl ether, heptyl acetate, and propylene glycol monomethyl ether.

10. The self-cleaning, wear-resistant, UV-curable coating according to claim 1, characterized in that, Z is selected from chain-like aliphatic groups with 1 to 11 carbon atoms.

11. The self-cleaning, wear-resistant, UV-curable coating according to claim 1, characterized in that, The leveling agent is at least one of BYK-306, BYK-307, BYK-333, BYK-354, BYK-377, Levaslip 407, Levaslip 410, Levaslip 411, Levaslip 432, and Levaslip 466.

12. The method for preparing the self-cleaning, wear-resistant, UV-curable coating according to any one of claims 1 to 11, characterized in that, The self-cleaning, wear-resistant, UV-curable coating is obtained by mixing acrylate resin, reactive diluent, photoinitiator, solvent, perfluoropolyether-modified long-fluorinated side-chain polyurethane acrylate, and leveling agent.

13. The application of the self-cleaning abrasion-resistant UV-curable coating according to any one of claims 1 to 11 in the preparation of a self-cleaning abrasion-resistant UV-curable coating.

14. A self-cleaning, wear-resistant, UV-curable coating, characterized in that, The coating is formed by forming a film from the self-cleaning, wear-resistant, UV-curable coating according to any one of claims 1 to 11, drying it, and then curing it under ultraviolet light.

15. A method for preparing a self-cleaning, wear-resistant, UV-curable coating, characterized in that, The self-cleaning and wear-resistant UV-curable coating according to any one of claims 1 to 11 is formed into a film, dried, and then cured under ultraviolet light to obtain the self-cleaning and wear-resistant UV-curable coating.

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