CN112011266A - UV (ultraviolet) curing coating, protective film comprising UV curing coating and preparation method of protective film - Google Patents

UV (ultraviolet) curing coating, protective film comprising UV curing coating and preparation method of protective film Download PDF

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CN112011266A
CN112011266A CN202011182207.7A CN202011182207A CN112011266A CN 112011266 A CN112011266 A CN 112011266A CN 202011182207 A CN202011182207 A CN 202011182207A CN 112011266 A CN112011266 A CN 112011266A
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coating
modified
protective film
curing
mofs
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CN112011266B (en
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朱小云
李友良
张家祯
陈喆
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Ningbo Funa New Materials Technology Co ltd
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Ningbo Funa New Materials Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a UV curing coating, a protective film containing the same and a preparation method of the protective film, wherein the protective film comprises a UV curing coating and a substrate layer which are sequentially laminated from top to bottom; the UV curing coating comprises the following components in percentage by weight: 18-45% of polyurethane acrylate; Ti-MOFs modified surface and isobutyl triethoxysilane modified nano silicon dioxide 0.5-3.5%; 0.5-1.5% of hydrophobic and oleophobic auxiliary agent; 0.5-2% of a dispersant; 0.5% -3% of a photoinitiator; 45% -80% of a solvent. According to the invention, the surface is modified by Ti-MOFs and the nano-silica modified by isobutyl triethoxysilane is added, so that a layer of crystalline porous structure with a periodic network is formed on the surface of the coating, and the structure has good characteristics of hydrophobicity and easy cleaning, so that the protective film disclosed by the invention can keep good performances of hydrophobicity, stain resistance, wear resistance and easy cleaning all the time in the using process.

Description

UV (ultraviolet) curing coating, protective film comprising UV curing coating and preparation method of protective film
Technical Field
The invention relates to the technical field of ultraviolet curing coatings, in particular to a hydrophobic stain-resistant long-acting wear-resistant UV curing coating taking Ti-MOFs modified isobutyl triethoxysilane modified nano-silica surface as an additive, a protective film containing the coating and a preparation method of the coating.
Background
The current UV nano coating is widely applied to the fields of mobile phones, automobiles, medical treatment and the like, and a layer of UV nano coating is processed on the surface of a product, so that the effect of beautifying the appearance can be achieved, and the hardness, the wear resistance, the acid and alkali resistance, the aging resistance and the like of the product can be greatly improved. For example, the surface of the mobile phone is easily polluted by oil stains and fingerprints in the using process and is difficult to clean, or the mobile phone is easily scratched and abraded after long-term use, and the problems can be well solved through the application of the UV coating.
The hydrophobic stain-resistant easy-cleaning performance of the existing hydrophobic wear-resistant coating can be quickly weakened and disappeared in the using process, and the comfort of a user in using the product is seriously influenced, so that the market urgently needs a UV nano coating which has the hydrophobic stain-resistant performance and can keep the hydrophobic stain-resistant performance for a long time in the using process.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the technical defect that the hydrophobic stain-resistant easy-to-clean performance of a coating in the prior art is rapidly weakened and disappeared in the using process, and provides a UV curing coating, a protective film comprising the UV curing coating and a preparation method of the UV curing coating. The UV curing coating provided by the invention has a hydrophobic stain-resistant long-acting wear-resistant function, the surface of the coating is modified by adding Ti-MOFs and the nano-silica modified by isobutyl triethoxysilane, so that a layer of crystalline porous structure with a periodic network is formed on the surface of the coating, the structure has good hydrophobic and easy-to-clean characteristics, and meanwhile, the coating has rigidity and flexibility due to the compounding of the Ti-MOFs modified nano-silica and a system, the wear-resistant performance of the coating is effectively improved, and the protective film can keep good hydrophobic stain-resistant and easy-to-clean performance all the time in the using process. The hydrophobic stain resistance of the coating is almost unchanged after certain dry grinding, wet grinding and solvent and detergent resistant friction; the hydrophobic stain-resistant UV curing coating is used for products of PMMA, PC, PCTG and other base materials, plays a role in well keeping good hydrophobic and oleophobic property and easy cleaning, and meanwhile, the adhesive force of the hydrophobic stain-resistant UV curing coating on the PMMA, PC, PCTG and other base materials can reach 5B, and the hydrophobic stain-resistant UV curing coating is high in surface hardness and good in wear resistance.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in a first aspect, the present invention provides a UV-curable coating comprising, in weight percent:
18-45% of polyurethane acrylate; Ti-MOFs modified surface and isobutyl triethoxysilane modified nano silicon dioxide 0.5-3.5%; 0.5-1.5% of hydrophobic and oleophobic auxiliary agent; 0.5-2% of a dispersant; 0.5% -3% of a photoinitiator; 45% -80% of a solvent.
According to the invention, the Ti-MOFs modified surface and the isobutyl triethoxy silane modified nano silicon dioxide are added, and the content of the nano silicon dioxide is controlled within the range of 0.5-3.5%, so that after the UV curing coating is subjected to ultraviolet curing, a composite nano coating with a periodic network crystalline porous structure can be formed on the surface of the coating, the wear resistance is excellent, and the water drop angle after grinding is high.
Further, the functionality of the polyurethane acrylate is 2-9, and preferably the functionality is 5-7.
Further, the polyurethane acrylate is obtained by mixing 6-functional polyurethane acrylate and 2-3-functional polyurethane acrylate.
Further, the diameter of the Ti-MOFs modified surface and the diameter of the isobutyl triethoxysilane modified nano-silica are 20-500 nm.
Further, the hydrophobic and oleophobic auxiliary agent is any one of fluorinated acrylic polymer, polyether siloxane copolymer and fluorine-containing modified organic silicon polyimide compound.
Further, the dispersant is at least one of a urethane copolymer, an acidic group-containing copolymer, a modified polyether acrylic polymer, and a high molecular weight block copolymer.
Further, the photoinitiator is at least one of cyclohexyl phenyl ketone (IRGACURE 184), 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide (TPO), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (819), and 2-hydroxy-2-methyl-1-phenyl-1-propanone (DAROCUR 1173).
Further, the solvent is at least three of ethyl acetate, acetone, methyl isobutyl ketone, diisobutyl ketone, propylene glycol methyl ether acetate, butyl acetate, propylene glycol methyl ether and isopropanol.
In a second aspect, the invention also provides a protective film, which comprises the UV-cured coating and the substrate layer which are sequentially laminated from top to bottom.
Furthermore, the material of the substrate layer is any one of PMMA, PC and PCTG.
In a third aspect, the present invention further provides a method for preparing the protective film, which specifically includes:
a. preparing Ti-MOFs modified surface and isobutyl triethoxysilane modified nano-silica: mixing Ti-MOFs, isobutyl triethoxy silane, nano silicon dioxide and butyl acetate in a weight ratio of 1: 1: 2: uniformly mixing and stirring the components in a proportion of 200, heating and stirring the components in a constant-temperature oil bath at the temperature of 80 ℃ until the solvent is volatilized to be dry, and obtaining the Ti-MOFs modified surface and the isobutyl triethoxysilane modified nano silicon dioxide;
b. preparation of UV curing coating: adding Ti-MOFs modified surface, isobutyl triethoxysilane modified nano-silica, a dispersing agent and polyurethane acrylate into a container according to the weight percentage, stirring for 20-60 min at the rotating speed of 1000-1500 r/min, then adding a hydrophobic and oleophobic auxiliary agent, stirring for 5-30 min at the rotating speed of 1000-1500 r/min, then adding a solvent, stirring for 20-120 min at the rotating speed of 1000-1500 r/min, adding a photoinitiator, continuously stirring for 5-30 min at the rotating speed of 1000-1500 r/min, and then performing ultrasound treatment for 20-60 min at the temperature of 20-30 ℃ to obtain the UV curing coating;
c. cleaning a substrate: cleaning and drying the surface of the substrate layer;
d. spraying: spraying the UV curing coating on the surface of a PMMA, PC, PCTG and other substrate layer;
e. and (3) drying: baking at 60-80 ℃ for 5 min; then curing the mixture in a UV curing machine, wherein the UV curing energy is 1500-2100 mJ/cm2。
In a fourth aspect, the invention also provides the application of the UV-cured coating in the first aspect, which is to spray the UV-cured coating on the surface of PMMA, PC, PCTG and other substrates, so as to endow the substrates with the characteristics of easy cleaning and stain resistance by hydrophobic and oleophobic properties.
The results of the hydrophobic and stain resistance tests and the oleophobic tests of the coating of the invention are as follows:
first, hydrophobic and stain resistance test:
(1) the initial water drop angle is more than or equal to 110 degrees, and the marker pen shrinks the ball and is easy to erase.
(2) After steel wool is rubbed: the coating was rubbed with a 1kg force, 0000# steel wool, Φ 1cm head, 2500 times in a reciprocating manner, the surface condition was visually inspected under light, and the hydrophobicity and the marker resistance of the rubbed portion were tested. Through testing, the UV curing coating prepared by the invention has no scratch on the surface after being rubbed for 2500 times, the water drop angle is more than or equal to 105 degrees after being rubbed for 2500 times, and the marker pens at the rubbed parts are easy to erase.
(3) Rubbing with a scouring pad: using 500 force, two layers of scouring pads, a grinding head with the diameter of 1cm rubs on the coating layer for 10000 times in a reciprocating manner, visually checking the surface condition under the light, and testing the hydrophobicity and the marker resistance of the rubbed part. Tests prove that the UV curing coating prepared by the invention has no scratch on the surface after being rubbed for 10000 times, the water drop angle is more than or equal to 100 degrees, and the marker pens at the rubbed part are easy to erase.
(4) After ethanol friction resistance: the two layers are soaked in the ethanol scouring pad with 1kg force, the surface of the coating is not scratched after 5000 times of reciprocating friction of a grinding head with the diameter of 1cm, the water drop angle is not less than 105 degrees after 5000 times of grinding, and the marker pen at the friction part is easy to erase.
(5) After the glass water friction resistance: the two layers are soaked in 20% glass water scouring pad with 1kg force, the surface of the coating is not scratched after 5000 times of reciprocating friction of a phi 1cm grinding head on the coating, the water drop angle is not less than 105 degrees after 5000 times of grinding, and the marker pen at the friction part is easy to erase.
And II, oleophobic testing: the oil drop angle is more than or equal to 70 degrees.
The basic principle of the invention is as follows:
according to the invention, Ti-MOFs is adopted to modify the surface of the nano-silica modified by isobutyl triethoxysilane, the nano-silica modified by Ti-MOFs and modified by isobutyl triethoxysilane is added into a UV nano-coating system to prepare the hydrophobic wear-resistant nano-coating, the surface of the coating forms a crystalline porous structure with a periodic network by Ti-MOFs, the hydrophobic stain resistance of the coating is improved, in addition, the wear resistance of the coating is effectively improved by adding the modified silica modified by Ti-MOFs, and the protective film disclosed by the invention can always keep good hydrophobic stain resistance and easy cleaning performance in the using process.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the existing formula, the hydrophobic stain-resistant long-acting wear-resistant UV curing coating provided by the invention has more lasting hydrophobic stain resistance, the Ti-MOFs modified surface and the isobutyltriethoxysilane modified nano-silica are added, so that a layer of crystalline porous structure with a periodic network is formed on the surface of the coating, the structure has good hydrophobic stain resistance, and meanwhile, the Ti-MOFs modified nano-silica effectively improves the wear resistance of the coating, so that the protective film can keep good hydrophobic stain-resistant easy-to-clean performance all the time in the using process;
(2) the hydrophobic stain resistance of the coating is almost unchanged after certain dry grinding, wet grinding and solvent and detergent resistant friction; the hydrophobic stain-resistant UV curing coating is used for products of PMMA, PC, PCTG and other base materials, plays a role in well keeping good hydrophobic and oleophobic property and easy cleaning, and meanwhile, the adhesive force of the hydrophobic stain-resistant UV curing coating on the PMMA, PC, PCTG and other base materials can reach 5B, and the hydrophobic stain-resistant UV curing coating is high in surface hardness and good in wear resistance.
Drawings
FIG. 1 is a schematic structural diagram of a protective film according to the present invention.
The corresponding part names for the various reference numbers in the figures are:
1-UV curing the coating; 2-a substrate layer.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings. It is to be understood that these examples are for further illustration of the invention and are not intended to limit the scope of the invention. In addition, it should be understood that the invention is not limited to the above-described embodiments, but is capable of various modifications and changes within the scope of the invention.
Example 1
As shown in fig. 1, the protective film of the present embodiment includes a UV curable coating layer 1 and a base material layer 2 laminated in this order from top to bottom.
The material of the substrate layer 2 is PC.
The UV curing coating 1 provided by the embodiment is a hydrophobic stain-resistant long-acting wear-resistant protective coating used for a plastic base material layer 2 such as PMMA, PC, PCTG and the like, plays a role in hydrophobic and oleophobic easy cleaning in the using process of a product, the adhesive force of the UV curing coating 1 on the base material layer 2 such as PMMA, PC, PCTG and the like can reach 5B, the surface hardness is high, the hydrophobic and oleophobic stain-resistant performance is good, and the UV curing coating 1 still keeps good hydrophobic property and stain resistance after dry grinding, wet grinding and solvent and detergent friction.
The UV-curable coating 1 of the present embodiment comprises the following components by weight percent as shown in table 1:
TABLE 1 compositional make-up of UV-cured coatings of examples 1-3 and comparative example 1
Figure 84983DEST_PATH_IMAGE001
The preparation method of the protective film comprising the UV curing coating 1 specifically comprises the following steps:
weighing raw materials according to the formula of the UV curing coating 1, adding the surface-modified nano-silica, the dispersing agent KOS163, the 6-functional polyurethane acrylate AgiSyn 242 and the 2-3-functional polyurethane acrylate YS-8806 in the weight percentage into a container, stirring for 30min at the rotating speed of 1000-1500 r/min, then adding the hydrophobic and oleophobic auxiliary agent TEGO Protect 5000N, stirring for 10min at the rotating speed of 1000-1500 r/min, then adding the solvent, stirring for 30min at the rotating speed of 1000-1500 r/min, then adding the photoinitiator, continuously stirring for 10min at the rotating speed of 1000-1500 r/min, and then carrying out ultrasonic treatment for 30min at the temperature of 20-30 ℃ to obtain the UV curing coating;
spraying the UV curing coating on the surface of a PC substrate, and baking for 5min at 70 ℃; then the passing energy is 1500-2100 mJ/cm2And curing the mixture by using a UV curing machine to form a transparent paint film. The physical testing of the painted surface was carried out and the results are shown in Table 2.
Example 2
This example is substantially the same as example 1 except that the formulation composition of the UV curable coating is different, the specific formulation composition is shown in table 1, and the test results are shown in table 2.
Example 3
This example is substantially the same as example 1 except that the formulation composition of the UV curable coating is different, the specific formulation composition is shown in table 1, and the test results are shown in table 2.
Comparative example 1
This comparative example is essentially the same as example 1 except that the formulation composition of the UV cured coating is different, the specific formulation composition is shown in table 1 and the test results are shown in table 2.
The initial water drop angle, oil drop angle, steel wool friction, scouring pad friction, ethanol friction resistance, glass water friction resistance, pencil hardness and adhesion of the coatings obtained in examples 1 to 3, comparative example 1 and the existing products on the market were measured, and the results are shown in table 2.
Table 2 physical property test table for painted surface of coating obtained in examples 1 to 3, comparative example 1 and conventional product
Test item Example 1 Example 2 Example 3 Comparative example 1 Existing hydrophobic wear-resistant coating in market
Initial water drop angle ≥110° ≥110° ≥110° ≥105° ≥105°
Oil drop angle ≥75° ≥75° ≥75° ≥65° ≥60°
Steel wool after friction drop angle (phi 1cm head, 0000# steel wool 1kgf, reciprocating friction 2500 times) ≥100° ≥105° ≥105° <70° <70°
Angle of water drop after rubbing with scouring pad (phi 1cm head, 500gf, toMultiple friction 1 ten thousand times) ≥100° ≥105° ≥105° <70° <70°
Resistance to Water droplet Angle after ethanol rub (phi 1cm indenter, 1kgf, reciprocal rub 5000 times) ≥105° ≥105° ≥105° <80° <80°
Resistance to water droplet angle after water rubbing of glass (phi 1cm indenter, 1kgf, reciprocal rubbing 5000 times) ≥100° ≥105° ≥105° <70° <70°
Pencil hardness (1 kgf, Mitsubishi pencil) H H H HB HB
Adhesion force 5B 5B 5B 5B 5B
As can be seen from Table 2, the initial hydrophobic properties of the UV cured coatings 1 prepared in examples 1-3 are all greater than or equal to 110 degrees through tests, and the coatings still maintain good hydrophobicity and stain resistance after steel wool friction, scouring pad friction, ethanol friction resistance and glass water friction resistance. The water drop angle of the hydrophobic wear-resistant coating in the comparative example 1 and the existing hydrophobic wear-resistant coating in the market is greatly reduced after steel wool friction, scouring pad friction, ethanol friction and glass water friction. Therefore, compared with the common hydrophobic and oleophobic wear-resistant coating in the market, the hydrophobic and oleophobic wear-resistant coating has the advantages that the surface of the coating still has good hydrophobic and stain resistance after being rubbed by various machines and solvents, and the coating can not only play a good role in wear resistance and scratch resistance when being applied to products such as mobile phones, automobiles, medical instruments and the like, but also is not easy to be stained with fingerprint oil stains in the long-term use process.
The water drop angles of the coating after 2500 times of friction of the steel wool of the existing products in the embodiment 2 and the comparative example 1 are compared. The result shows that the water drop angle of the coating after 2500 times of friction of the steel wool in the example 2 is 106.824 degrees, the water drop angle of the coating after 2500 times of friction of the steel wool in the comparative example 1 is 64.252 degrees, and the water drop angle of the coating after 2500 times of friction of the existing hydrophobic and oleophobic wear-resistant coating steel wool in the market is 66.863 degrees. Therefore, the water drop angle of the coated steel wool prepared in the example 2 of the invention after friction is far better than that of the comparative example 1 and the existing products in the market.
The water drop angles of the coating after 5000 times of ethanol friction resistance of the existing products in the market, which are obtained in example 2 and comparative example 1 of the invention, are compared. The result shows that the water drop angle of the coating after 5000 times of ethanol friction resistance of the example 2 is 108.078 degrees, the water drop angle of the coating after 5000 times of ethanol friction resistance of the comparative example 1 is 73.689 degrees, and the water drop angle of the coating after 5000 times of ethanol friction resistance of the existing hydrophobic and oleophobic wear-resistant coating on the market is 71.030 degrees. From this, it can be seen that the water drop angle of the coating prepared in example 2 of the present invention after ethanol rubbing is far superior to that of comparative example 1 and the existing products in the market.
From the above, it can be seen that example 2 still maintains good hydrophobicity after a series of friction tests, which indicates that the coating can maintain good hydrophobic stain resistance in the using process, because the coating prepared by adding Ti-MOFs modified and isobutyltriethoxysilane modified nano-silica to the UV nano-coating system forms a layer of crystalline porous structure with periodic network on the surface by Ti-MOFs, the hydrophobic stain resistance of the coating is improved, and in addition, the addition of Ti-MOFs modified silica effectively improves the wear resistance of the coating, so that the coating of the present invention can maintain good hydrophobic stain resistance and easy cleaning performance all the time in the using process. In contrast, in comparative example 1, since the nano-silica modified with Ti-MOFs and modified with isobutyltriethoxysilane was not added, the hydrophobic stain resistance was rapidly decreased during the use.
The product of example 2 was compared after the oily marker marks on the rubbed part and the paper were erased, and the oily marker marks on the rubbed part of the existing coating on the market and the paper were erased. The results show that the invention can easily erase the oil-based marker marks, and the existing products in the market are not easy to erase the oil-based marker marks. It can be seen that the UV cured coating 1 of the present invention has significantly better stain resistance.
According to the UV curing coating 1 provided by the invention, the surface is modified by Ti-MOFs and the nano-silica modified by isobutyl triethoxysilane is added, so that a layer of crystalline porous structure with a periodic network is formed on the surface of the coating, the structure has good hydrophobic and easy-to-clean characteristics, and meanwhile, the Ti-MOFs modified silica is compounded with the system, so that the coating has rigidity and flexibility, the wear resistance of the coating is effectively improved, and the coating still keeps good hydrophobic and stain resistance after being subjected to dry grinding, wet grinding and solvent and detergent resistant friction.
The hydrophobic stain resistance of the coating is almost unchanged after certain dry grinding, wet grinding and solvent and detergent resistant friction; the hydrophobic stain-resistant UV curing coating is used for products of PMMA, PC, PCTG and other base materials, plays a role in well keeping good hydrophobic and oleophobic property and easy cleaning, has the adhesion force of 5B on the PMMA, PC, PCTG and other base materials, and has high surface hardness and good wear resistance.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.

Claims (10)

1. The UV-cured coating is characterized by comprising the following components in percentage by weight:
18-45% of polyurethane acrylate; Ti-MOFs modified surface and isobutyl triethoxysilane modified nano silicon dioxide 0.5-3.5%; 0.5-1.5% of hydrophobic and oleophobic auxiliary agent; 0.5-2% of a dispersant; 0.5% -3% of a photoinitiator; 45% -80% of a solvent.
2. The UV-curable coating of claim 1, wherein the urethane acrylate has a functionality of 2 to 9.
3. The UV-curable coating of claim 1, wherein the Ti-MOFs modified surface and the isobutyltriethoxysilane modified nanosilica have a diameter of 20-500 nm.
4. The UV-curable coating according to claim 1, wherein the hydrophobic and oleophobic auxiliary agent is any one of fluorinated acrylic polymer, polyether siloxane copolymer, and fluorine-containing modified organic silicon polyimide.
5. The UV-curable coating of claim 1, wherein the dispersant is at least one of a urethane copolymer, an acidic group-containing copolymer, a modified polyether acrylic polymer, and a high molecular weight block copolymer.
6. The UV-curable coating of claim 1, wherein the photoinitiator is at least one of cyclohexylphenyl ketone, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone.
7. The UV-curable coating according to claim 1, wherein the solvent is at least three of ethyl acetate, acetone, methyl isobutyl ketone, diisobutyl ketone, propylene glycol methyl ether acetate, butyl acetate, propylene glycol methyl ether, and isopropyl alcohol.
8. A protective film comprising the UV-curable coating layer (1) according to any one of claims 1 to 7 and a substrate layer (2) laminated in this order from the top.
9. A protective film according to claim 8, wherein the material of the substrate layer (2) is any one of PMMA, PC and PCTG.
10. The method for producing a protective film according to claim 8, comprising the steps of:
a. preparing Ti-MOFs modified surface and isobutyl triethoxysilane modified nano-silica: mixing Ti-MOFs, isobutyl triethoxy silane, nano silicon dioxide and butyl acetate in a weight ratio of 1: 1: 2: uniformly mixing and stirring the components in a proportion of 200, heating and stirring the components in a constant-temperature oil bath at the temperature of 80 ℃ until the solvent is volatilized to be dry, and obtaining the Ti-MOFs modified surface and the isobutyl triethoxysilane modified nano silicon dioxide;
b. preparation of UV curing coating: adding Ti-MOFs modified surface, isobutyl triethoxysilane modified nano-silica, a dispersing agent and polyurethane acrylate into a container according to the weight percentage, stirring for 20-60 min at the rotating speed of 1000-1500 r/min, then adding a hydrophobic and oleophobic auxiliary agent, stirring for 5-30 min at the rotating speed of 1000-1500 r/min, then adding a solvent, stirring for 20-120 min at the rotating speed of 1000-1500 r/min, adding a photoinitiator, continuously stirring for 5-30 min at the rotating speed of 1000-1500 r/min, and then performing ultrasound treatment for 20-60 min at the temperature of 20-30 ℃ to obtain the UV curing coating;
c. cleaning a substrate: cleaning and drying the surface of the substrate layer (2);
d. spraying: spraying the UV curing coating on the surface of the substrate layer (2);
e. and (3) drying: baking at 60-80 ℃ for 5 min; then curing the mixture in a UV curing machine, wherein the UV curing energy is 1500-2100 mJ/cm2。
CN202011182207.7A 2020-10-29 2020-10-29 UV (ultraviolet) curing coating, protective film comprising UV curing coating and preparation method of protective film Active CN112011266B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113386429A (en) * 2021-04-06 2021-09-14 安徽禾臣新材料有限公司 Self-cleaning film for electronic display screen and preparation method thereof
CN114196031A (en) * 2021-09-04 2022-03-18 桂林理工大学 Preparation method and application of POTS (plain old telephone service) super-hydrophobic modified material based on thiophene MOFs (metal-organic frameworks)
CN115231835A (en) * 2022-09-19 2022-10-25 江苏中新瑞光学材料有限公司 Preparation method of UV (ultraviolet) curing super-hydrophobic material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113386429A (en) * 2021-04-06 2021-09-14 安徽禾臣新材料有限公司 Self-cleaning film for electronic display screen and preparation method thereof
CN114196031A (en) * 2021-09-04 2022-03-18 桂林理工大学 Preparation method and application of POTS (plain old telephone service) super-hydrophobic modified material based on thiophene MOFs (metal-organic frameworks)
CN115231835A (en) * 2022-09-19 2022-10-25 江苏中新瑞光学材料有限公司 Preparation method of UV (ultraviolet) curing super-hydrophobic material
CN115231835B (en) * 2022-09-19 2022-12-02 江苏中新瑞光学材料有限公司 Preparation method of UV (ultraviolet) curing super-hydrophobic material

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