CN113061391A - Radiation-cured antifogging coating composition and film and preparation method thereof - Google Patents
Radiation-cured antifogging coating composition and film and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/6715—Unsaturated monofunctional alcohols or amines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
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- 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
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- 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
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- 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
- C08J7/054—Forming anti-misting or drip-proofing coatings
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- 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
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The invention provides a radiation-cured antifogging coating composition and a film and a preparation method thereof, wherein methoxypolyethylene glycol acetic acid is esterified with glycerol, unsaturated dihydric alcohol is added, the temperature is reduced after vacuum dehydration at high temperature, a diluting monomer and a catalyst are added, the temperature is raised, diisocyanate is added dropwise and stirred, unsaturated monohydric alcohol and a polymerization inhibitor are added, and the rest components are added to obtain the antifogging coating composition which is then coated on the film and is subjected to radiation curing to obtain the film with antifogging performance. According to the invention, a hydrophilic polyethylene glycol chain segment is reacted onto a polyurethane main chain in a branched chain form, the main chain is mainly of a repeating structure of unsaturated dihydric alcohol and diisocyanate, and is terminated by unsaturated monohydric alcohol to form a radiation-curable antifogging coating composition, the antifogging coating composition is well attached to the surface of an untreated plastic base material through radiation curing, and the antifogging coating has good light transmittance, antifogging property, hardness, friction resistance and water resistance.
Description
Technical Field
The invention belongs to the field of radiation curing coating, relates to an antifogging coating, and particularly relates to a radiation curing antifogging coating composition, a radiation curing antifogging coating film and a preparation method thereof.
Background
In daily life, the phenomenon of fogging of automobile rearview mirrors, automobile windows, helmet eyeshields or glasses is frequently encountered, the sight of people is seriously influenced, and normal life and work are hindered. Therefore, a plurality of antifogging coatings are produced, and the antifogging coatings can be divided into two types in the process, wherein one type is water-based paint which needs to be heated and baked to achieve surface drying or curing so as to realize antifogging performance; the other is UV light-cured paint, and the solvent also needs to be removed by heating and then UV light-cured to realize antifogging property. Both the hydrophilic groups are adopted, the hydrophilic groups float to the surface in the heating process to form a top layer whole hydrophilic chain segment, and a bottom layer oleophylic chain segment is crosslinked and cured to achieve certain hardness and water resistance. However, both the two processes require a longer drying tunnel, have high energy consumption and certain VOC emission, and are not beneficial to environmental protection and personal safety of constructors.
Therefore, the development of a novel antifogging coating composition and process which has zero VOC emission, low energy consumption and environmental protection is particularly important, and has more important economic value and use value.
Disclosure of Invention
Aiming at the defects, the invention provides a radiation-cured antifogging coating composition, a radiation-cured antifogging coating film and a preparation method thereof, and the preparation method and the implementation method of the radiation-cured antifogging coating can effectively solve the VOC emission problem, reduce the energy consumption and greatly improve the durability and the water resistance of the antifogging coating.
The invention provides the following technical scheme: a radiation-cured antifogging coating composition comprises the following components in parts by weight:
further, the molecular weight of the methoxypolyethylene glycol acetic acid is 1000-5000.
Further, the first catalyst is one or more of antioxidant 1010 tetra [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid ] pentaerythritol ester, antioxidant 168 tri (2, 4-di-tert-butylphenyl) phosphite and antioxidant 1076 beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid n-octadecyl ester;
the second antioxidant is one or more of antioxidant 1010 tetra [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid ] pentaerythritol ester, antioxidant 168 tri (2, 4-di-tert-butylphenyl) phosphite and antioxidant 1076 beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid n-octadecyl ester.
Further, the unsaturated dihydric alcohol is one or more of trimethylolpropane monoallyl ether, 1, 4-butylene glycol, 3-hexene-1, 6 diol, 1, 4-butynediol, 2, 4-hexadiyne-1, 6 diol and 2, 5-dimethylhexynediol;
the unsaturated monohydric alcohol is one or more of 4-hydroxybutyl vinyl ether, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, allyl alcohol and 3-butene-1-alcohol.
Further, the diluent monomer is one or more of tetrahydrofuran acrylate, tetrahydrofuran methacrylate, dicyclopentenyl acrylate, cyclotrimethylolpropane acroacetal acrylate, cyclohexyl methacrylate, 1, 6-hexanediol diacrylate and 1, 6-hexanediol dimethacrylate.
Further, the first catalyst is one or more of stannous chloride, stannous octoate and stannous oxide;
the second catalyst is one or more of stannous chloride, stannous octoate and stannous oxide.
Further, the diisocyanate is one or more of Hexamethylene Diisocyanate (HDI), IsoFriedel diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI); the polymerization inhibitor is one of hydroquinone, 2-tert-butyl hydroquinone, methyl hydroquinone and 4-methoxyphenol.
The invention also provides a radiation-cured antifogging coating film prepared by adopting the coating composition.
The invention also provides a preparation method of the film with the radiation curing antifogging coating, which comprises the following steps:
s1: adding the methoxypolyethylene glycol acetic acid, the glycerol, the first catalyst and the first antioxidant into a reactor, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, and vacuumizing for 1 hour;
s2: when the acid value of the product generated in the step S1 reaches 0.1-0.5, cooling to 100 ℃, adding the unsaturated diol in parts by weight, and dehydrating in vacuum at 100-130 ℃ for 1 hour;
s3: adding the diluted monomer and the second catalyst in parts by weight into the mixture obtained in the step S2, dropwise adding the diisocyanate in parts by weight at 70-80 ℃, and after dropwise adding, stirring for 2 hours at 80 ℃;
s4: when the NCO content in the product obtained in the step S3 is measured to be between 0.1 and 5 percent, the polymerization inhibitor and the unsaturated monohydric alcohol are added in parts by weight, and the mixture is stirred for 2 hours at the temperature of 80 ℃;
s5: adding the second antioxidant in parts by weight, the ultraviolet light absorber in parts by weight, the light stabilizer in parts by weight, the leveling agent in parts by weight and the defoaming agent in parts by weight into the mixture obtained in the step S4, and uniformly stirring to obtain an antifogging coating composition;
s6: and coating the antifogging coating composition obtained in the step S5 on a substrate material, and forming a film through radiation curing under the protection of nitrogen to obtain the film with the radiation-cured antifogging coating.
Further, the radiation curing equipment used in step S6 is a UV mercury lamp, a UV led or an EB electron beam, and a photoinitiator, which may be a radical photoinitiator or a cationic photoinitiator, such as 184, TPO, 1173, 6992/6976; the substrate material is one of polyethylene terephthalate (PET), Polycarbonate (PC) and polymethyl methacrylate (PMMA).
The principle of the invention is as follows: the invention firstly esterifies methoxy polyethylene glycol acetic acid and glycerin to obtain a product A containing dihydric alcohol, and the reaction process is as follows:
this product a is then introduced in branched form onto the polyurethane backbone, the reaction being as follows:
the branched chain is a reaction product A of mPEG-AA and glycerol, n is the polymerization degree of mPEG-AA, R is diisocyanate, B is unsaturated dihydric alcohol, the main chain is a repeating unit of diisocyanate R, B, mPEG-AA and a polymer A of glycerol, m is the polymerization degree of the repeating unit, and finally the product C is blocked by unsaturated monohydric alcohol to form the radiation-cured antifogging coating composition.
The invention has the beneficial effects that:
the preparation components of the antifogging coating provided by the invention are coated on an untreated PET film, an oleophylic main chain is flatly laid on the PET film, hydrophilic branched chains are completely distributed on the upper layer of the composition to be contacted with air, and then unsaturated double bonds in the main chain are crosslinked and cured through EB electron beam or UV light radiation to form the antifogging coating with certain hardness, and the adhesive force reaches 0 grade of Baige. The antifogging coating adopts an EB (Electron Beam) or UV (ultraviolet) radiation curing mode, a free radical initiator does not need to be added, the coating cost can be reduced, no solvent is contained, VOC (volatile organic compounds) is zero, no oven is needed, the energy consumption is low, the production cost is low, and the environment-friendly requirement is compounded.
The preparation method of the radiation-cured antifogging coating provided by the invention enables the antifogging coating to have good antifogging performance, light transmittance, firmness, water resistance, friction resistance and hardness on a PET (polyethylene terephthalate) substrate, and the antifogging performance can be as long as 2 years.
Detailed description of the preferred embodiments
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following examples use the names of the compounds (all of which are commercially available starting materials):
mPEG-AA 1000: methoxypolyethylene glycol acetic acid (molecular weight 1000)
mPEG-AA 2000: methoxypolyethylene glycol acetic acid (molecular weight 2000)
mPEG-AA 3000: methoxypolyethylene glycol acetic acid (molecular weight 3000)
mPEG-AA 4000: methoxypolyethylene glycol acetic acid (molecular weight 4000)
mPEG-AA 5000: methoxypolyethylene glycol acetic acid (molecular weight 5000)
Glycerol: glycerol
Catalyst: stannous octoate
Antioxidant 168: tris (2, 4-di-tert-butylphenyl) phosphite
Unsaturated dihydric alcohol: 3-hexene-1, 6 diol
Diluting monomers: cyclotrimethylolpropane propaneacetal acrylate
Polymerization inhibitor MEHQ 4-methoxyphenol
HMDI: dicyclohexylmethane diisocyanate
Unsaturated monohydric alcohol: hydroxypropyl methacrylate
Defoaming agent BYK1790
Leveling agent BYK333
Ultraviolet absorber constant bridge chemical 1130
Light stabilizer constant bridge chemical LS622
Example 1
Adding 20g of mPEG-AA1000, 1.84g of glycerol, 0.02g of stannous octoate and 0.02g of antioxidant 168 into a four-neck flask, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, vacuumizing for 1 hour, reducing the temperature to 100 ℃, adding 2.32g of 3-hexene-1, 6-diol, vacuum dehydrating for 1 hour at 120 ℃, adding 63g of cyclotrimethylolpropane propylene acetal acrylate and 0.1g of stannous octoate, dropwise adding 11.66g of HMDI at 70 ℃, keeping the temperature and stirring for 2 hours at 80 ℃ after dropwise adding, measuring the NCO content to 0.37%, adding 0.1g of MEHQ and 1.15g of hydroxypropyl methacrylate, keeping the temperature and stirring for 2 hours at 80 ℃, finally adding 0.1g of antioxidant 168, 0.5g of 1130, 0.5g of LS622, 0.1g of 1790 and 0.1g of antioxidant 333, and uniformly stirring to obtain the coating composition. The antifog coating composition was coated on an untreated PET substrate using an EB cure at a voltage of 120kv and a dose of 100 KGy.
Example 2
Adding 20g of mPEG-AA2000, 0.92g of glycerol, 0.02g of stannous octoate and 0.02g of antioxidant 168 into a four-neck flask, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, vacuumizing for 1 hour, reducing the temperature to 100 ℃, adding 3.48g of 3-hexene-1, 6-diol, vacuum dehydrating for 1 hour at 120 ℃, adding 63g of cyclotrimethylolpropane propylene acetal acrylate and 0.1g of stannous octoate, dropwise adding 11.66g of HMDI at 70 ℃, keeping the temperature and stirring for 2 hours at 80 ℃ after dropwise adding, measuring the NCO content to 0.37%, adding 0.1g of MEHQ and 1.15g of hydroxypropyl methacrylate, keeping the temperature and stirring for 2 hours at 80 ℃, finally adding 0.1g of antioxidant 168, 0.5g of 1130, 0.5g of LS622, 0.1g of 1790 and 0.1g of antioxidant 333, and uniformly stirring to obtain the coating composition. The antifog coating composition was coated on an untreated PET substrate using an EB cure at a voltage of 120kv and a dose of 100 KGy.
Example 3
Adding 20g of mPEG-AA3000, 0.61g of glycerol, 0.02g of stannous octoate and 0.02g of antioxidant 168 into a four-neck flask, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, vacuumizing for 1 hour, reducing the temperature to 100 ℃, adding 3.87g of 3-hexene-1, 6-diol, vacuum dehydrating for 1 hour at 120 ℃, adding 63g of cyclotrimethylolpropane propylene acetal acrylate and 0.1g of stannous octoate, dropwise adding 11.66g of HMDI at 70 ℃, keeping the temperature and stirring for 2 hours at 80 ℃ after dropwise adding, measuring the NCO content to 0.37%, adding 0.1g of MEHQ and 1.15g of hydroxypropyl methacrylate, keeping the temperature and stirring for 2 hours at 80 ℃, finally adding 0.1g of antioxidant 168, 0.5g of 1130, 0.5g of LS622, 0.1g of 1790 and 0.1g of antioxidant 333, and uniformly stirring to obtain the coating composition. The antifog coating composition was coated on an untreated PET substrate using an EB cure at a voltage of 120kv and a dose of 100 KGy.
Example 4
Adding 20g of mPEG-AA4000, 0.46g of glycerol, 0.02g of stannous octoate and 0.02g of antioxidant 168 into a four-neck flask, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, vacuumizing for 1 hour, reducing the temperature to 100 ℃, adding 4.06g of 3-hexene-1, 6-diol, vacuum dehydrating for 1 hour at 120 ℃, adding 63g of cyclotrimethylolpropane propylene acetal acrylate and 0.1g of stannous octoate, dropwise adding 11.66g of HMDI at 70 ℃, keeping the temperature and stirring for 2 hours at 80 ℃ after dropwise adding, measuring the NCO content to 0.37%, adding 0.1g of MEHQ and 1.15g of hydroxypropyl methacrylate, keeping the temperature and stirring for 2 hours at 80 ℃, finally adding 0.1g of antioxidant 168, 0.5g of 1130, 0.5g of LS622, 0.1g of 1790 and 0.1g of antioxidant 333, and uniformly stirring to obtain the coating composition. The antifog coating composition was coated on an untreated PET substrate using an EB cure at a voltage of 120kv and a dose of 100 KGy.
Example 5
Adding 20g of mPEG-AA5000, 0.36g of glycerol, 0.02g of stannous octoate and 0.02g of antioxidant 168 into a four-neck flask, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, vacuumizing for 1 hour, reducing the temperature to 100 ℃, adding 4.18g of 3-hexene-1, 6-diol, vacuum dehydrating for 1 hour at 120 ℃, adding 63g of cyclotrimethylolpropane propylene acetal acrylate and 0.1g of stannous octoate, dropwise adding 11.66g of HMDI at 70 ℃, keeping the temperature and stirring for 2 hours at 80 ℃ after dropwise adding, measuring the NCO content to 0.37%, adding 0.1g of MEHQ and 1.15g of hydroxypropyl methacrylate, keeping the temperature and stirring for 2 hours at 80 ℃, finally adding 0.1g of antioxidant 168, 0.5g of 1130, 0.5g of LS622, 0.1g of 1790 and 0.1g of antioxidant 333, and uniformly stirring to obtain the coating composition. The antifog coating composition was coated on an untreated PET substrate using an EB cure at a voltage of 120kv and a dose of 100 KGy.
The results of the performance tests on the antifog coatings prepared in examples 1-5 of the present invention are shown in table 1.
From the test results in table 1, it can be seen that the radiation-cured anti-fog coating composition of the present invention can have excellent adhesion and good hardness on the untreated PET film, and examples 1 to 5 have substantially better water resistance. In the same adding amount of mPEG-AA, the water contact angle is not reduced along with the increase of the molecular weight, but the pencil hardness and the friction resistance are in direct proportion to the molecular weight, because the higher the molecular weight of mPEG-AA, the lower the light transmittance, the lower the water contact angle after RA and QUV, the antifogging coating has longer service life, and the result of the comprehensive experiments shows that the mPEG-AA molecular weight of 2000 or 3000 is most suitable, and the invention takes the molecular weight of 2000 as an example to carry out the comparative experiments of comparative examples 1-5.
Comparative example 1
Adding 25g of mPEG-AA2000, 1.15g of glycerol, 0.02g of stannous octoate and 0.02g of antioxidant 168 into a four-neck flask, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, vacuumizing for 1 hour, reducing the temperature to 100 ℃, adding 3.48g of 3-hexene-1, 6-diol, vacuum dehydrating for 1 hour at 120 ℃, adding 63g of cyclotrimethylolpropane propylene acetal acrylate and 0.1g of stannous octoate, dropwise adding 12.39g of HMDI at 70 ℃, keeping the temperature and stirring for 2 hours at 80 ℃ after dropwise adding, measuring the NCO content to 0.37%, adding 0.1g of MEHQ and 1.36g of hydroxypropyl methacrylate, keeping the temperature and stirring for 2 hours at 80 ℃, finally adding 0.1g of antioxidant 168, 0.5g of 1130, 0.5g of LS622, 0.1g of 1790 and 0.1g of antioxidant 333, and uniformly stirring to obtain the coating composition. The antifog coating composition was coated on an untreated PET substrate using an EB cure at a voltage of 120kv and a dose of 100 KGy.
Comparative example 2
Adding 30g of mPEG-AA2000, 1.38g of glycerol, 0.02g of stannous octoate and 0.02g of antioxidant 168 into a four-neck flask, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, vacuumizing for 1 hour, reducing the temperature to 100 ℃, adding 3.48g of 3-hexene-1, 6-diol, vacuum dehydrating for 1 hour at 120 ℃, adding 63g of cyclotrimethylolpropane propylene acetal acrylate and 0.1g of stannous octoate, dropwise adding 13.1g of HMDI at 70 ℃, keeping the temperature and stirring for 2 hours at 80 ℃ after dropwise adding, measuring the NCO content to 0.37%, adding 0.1g of MEHQ and 1.44g of hydroxypropyl methacrylate, keeping the temperature and stirring for 2 hours at 80 ℃, finally adding 0.1g of antioxidant 168, 0.5g of 1130, 0.5g of LS622, 0.1g of 1790 and 0.1g of antioxidant, and uniformly stirring to obtain the coating composition. The antifog coating composition was coated on an untreated PET substrate using an EB cure at a voltage of 120kv and a dose of 100 KGy.
Comparative example 3
Adding 35g of mPEG-AA2000, 1.61g of glycerol, 0.02g of stannous octoate and 0.02g of antioxidant 168 into a four-neck flask, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, vacuumizing for 1 hour, reducing the temperature to 100 ℃, adding 3.48g of 3-hexene-1, 6-diol, vacuum dehydrating for 1 hour at 120 ℃, adding 63g of cyclotrimethylolpropane propylene acetal acrylate and 0.1g of stannous octoate, dropwise adding 13.84g of HMDI at 70 ℃, keeping the temperature and stirring for 2 hours at 80 ℃ after dropwise adding, measuring the NCO content to 0.38%, adding 0.1g of MEHQ and 1.52g of hydroxypropyl methacrylate, keeping the temperature and stirring for 2 hours at 80 ℃, finally adding 0.1g of antioxidant 168, 0.5g of 1130, 0.5g of LS622, 0.1g of 1790 and 0.1g of antioxidant 333, and uniformly stirring to obtain the coating composition. The antifog coating composition was coated on an untreated PET substrate using an EB cure at a voltage of 120kv and a dose of 100 KGy.
Comparative example 4
Adding 40g of mPEG-AA2000, 1.84g of glycerol, 0.02g of stannous octoate and 0.02g of antioxidant 168 into a four-neck flask, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, vacuumizing for 1 hour, reducing the temperature to 100 ℃, adding 3.48g of 3-hexene-1, 6-diol, vacuum dehydrating for 1 hour at 120 ℃, adding 63g of cyclotrimethylolpropane propylene acetal acrylate and 0.1g of stannous octoate, dropwise adding 14.57g of HMDI at 70 ℃, keeping the temperature and stirring for 2 hours at 80 ℃ after dropwise adding, measuring the NCO content to 0.38%, adding 0.1g of MEHQ and 1.6g of hydroxypropyl methacrylate, keeping the temperature and stirring for 2 hours at 80 ℃, finally adding 0.1g of antioxidant 168, 0.5g of 1130, 0.5g of LS622, 0.1g of 1790 and 0.1g of antioxidant 333, and uniformly stirring to obtain the coating composition. The antifog coating composition was coated on an untreated PET substrate using an EB cure at a voltage of 120kv and a dose of 100 KGy.
Comparative example 5
Adding 45g of mPEG-AA2000, 2.07g of glycerol, 0.02g of stannous octoate and 0.02g of antioxidant 168 into a four-neck flask, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, vacuumizing for 1 hour, reducing the temperature to 100 ℃, adding 3.48g of 3-hexene-1, 6-diol, vacuum dehydrating for 1 hour at 120 ℃, adding 63g of cyclotrimethylolpropane propylene acetal acrylate and 0.1g of stannous octoate, dropwise adding 15.3g of HMDI at 70 ℃, keeping the temperature and stirring for 2 hours at 80 ℃ after dropwise adding, measuring the NCO content to 0.38%, adding 0.1g of MEHQ and 1.68g of hydroxypropyl methacrylate, keeping the temperature and stirring for 2 hours at 80 ℃, finally adding 0.1g of antioxidant 168, 0.5g of 1130, 0.5g of LS622, 0.1g of 1790 and 0.1g of antioxidant 333, and uniformly stirring to obtain the coating composition. The antifog coating composition was coated on an untreated PET substrate using an EB cure at a voltage of 120kv and a dose of 100 KGy.
The results of the performance tests of the antifog coatings prepared in inventive example 2 and comparative examples 1-5 are shown in table 2.
From the test results in table 2, the addition amount of mPEG-AA2000 is in direct proportion to the antifogging property, but is in inverse proportion to pencil hardness, adhesion, light transmittance, wear resistance, water resistance and aging resistance, and the antifogging coating can be judged to be effective within 2 years of indoor use through the water contact angle test results after RA and QUV. Comprehensively, the optimum proportion is that mPEG-AA2000 molecular weight is adopted, and the addition amount is about 26.7%.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. The radiation-cured antifogging coating composition is characterized by comprising the following components in parts by weight:
2. the radiation-curable antifogging coating composition of claim 1, wherein said methoxypolyethylene glycol acetic acid has a molecular weight of 1000 to 5000.
3. The radiation-curable antifog coating composition according to claim 1, wherein said first catalyst is one or more of antioxidant 1010 tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] pentaerythritol ester, antioxidant 168 tris (2, 4-di-tert-butylphenyl) phosphite, antioxidant 1076 n-octadecyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoate;
the second antioxidant is one or more of antioxidant 1010 tetra [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid ] pentaerythritol ester, antioxidant 168 tri (2, 4-di-tert-butylphenyl) phosphite and antioxidant 1076 beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid n-octadecyl ester.
4. The radiation-curable antifog coating composition of claim 1, wherein said unsaturated diol is one or more of trimethylolpropane monoallyl ether, 1, 4-butenediol, 3-hexene-1, 6 diol, 1, 4-butynediol, 2, 4-hexadiyne-1, 6 diol, 2, 5-dimethylhexynediol;
the unsaturated monohydric alcohol is one or more of 4-hydroxybutyl vinyl ether, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, allyl alcohol and 3-butene-1-alcohol.
5. The radiation-cured antifog coating composition of claim 1, wherein said diluent monomer is one or more of tetrahydrofuran acrylate, tetrahydrofuran methacrylate, dicyclopentenyl acrylate, cyclotrimethylolpropane acetal acrylate, cyclohexyl methacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate.
6. The radiation-cured antifog coating composition of claim 1, wherein said first catalyst is one or more of stannous chloride, stannous octoate, stannous oxide;
the second catalyst is one or more of stannous chloride, stannous octoate and stannous oxide.
7. The radiation-curable antifog coating composition of claim 1, wherein said diisocyanate is one or more of hexamethylene diisocyanate, isoflurane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate; the polymerization inhibitor is one of hydroquinone, 2-tert-butyl hydroquinone, methyl hydroquinone and 4-methoxyphenol.
8. A radiation-cured antifog coating film prepared with the coating composition according to any of claims 1 to 7.
9. The method for preparing a film with a radiation-cured antifogging coating according to claim 8, characterized in that it comprises the following steps:
s1: adding the methoxypolyethylene glycol acetic acid, the glycerol, the first catalyst and the first antioxidant into a reactor, heating to 130 ℃, heating to 5 ℃ every 10 minutes, heating to 220 ℃, keeping the temperature, stirring for 1 hour, and vacuumizing for 1 hour;
s2: when the acid value of the product generated in the step S1 reaches 0.1-0.5, cooling to 100 ℃, adding the unsaturated diol in parts by weight, and dehydrating in vacuum at 100-130 ℃ for 1 hour;
s3: adding the diluted monomer and the second catalyst in parts by weight into the mixture obtained in the step S2, dropwise adding the diisocyanate in parts by weight at 70-80 ℃, and after dropwise adding, stirring for 2 hours at 80 ℃;
s4: when the NCO content in the product obtained in the step S3 is measured to be between 0.1 and 5 percent, the polymerization inhibitor and the unsaturated monohydric alcohol are added in parts by weight, and the mixture is stirred for 2 hours at the temperature of 80 ℃;
s5: adding the second antioxidant in parts by weight, the ultraviolet light absorber in parts by weight, the light stabilizer in parts by weight, the leveling agent in parts by weight and the defoaming agent in parts by weight into the mixture obtained in the step S4, and uniformly stirring to obtain an antifogging coating composition;
s6: and coating the antifogging coating composition obtained in the step S5 on a substrate material, and forming a film through radiation curing under the protection of nitrogen to obtain the film with the radiation-cured antifogging coating.
10. The method for preparing the radiation-cured antifogging coating according to claim 9, wherein the radiation curing equipment used in step S6 is a UV mercury lamp, a UVLED or an EB electron beam, and a photoinitiator must be added for curing by UV light; the substrate material is one of polyethylene terephthalate, polycarbonate and methyl methacrylate.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2006019175A1 (en) * | 2004-08-19 | 2008-05-08 | 関西ペイント株式会社 | Photocurable composition for antifogging film formation |
| CN101489948A (en) * | 2006-08-23 | 2009-07-22 | 中央硝子株式会社 | Non-fogging preproduction, non-fogging articles and coating fluid for the articles |
| CN101602913A (en) * | 2009-06-26 | 2009-12-16 | 广州慧谷化学有限公司 | A kind of ultraviolet light curing anti fogging coating composite and compound method thereof |
| CN106118173A (en) * | 2016-07-28 | 2016-11-16 | 上海维凯光电新材料有限公司 | Hydrophilic antifogging coating composition of photo-thermal dual curable and preparation method thereof |
| EP3115387A1 (en) * | 2015-07-08 | 2017-01-11 | Universiteit Gent | Novel urethane based materials, derivatives, methods of their preparation and uses |
| CN106752857A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of the super hydrophilic antifogging coating of dual cure acrylate |
| CN107513345A (en) * | 2017-09-19 | 2017-12-26 | 上海纵港广告器材股份有限公司 | A kind of preparation method of unsaturated type polyurethane coating |
| US20180194890A1 (en) * | 2015-07-08 | 2018-07-12 | Universiteit Gent | Novel urethane based materials, derivatives, methods of their preparation and uses |
| CN108463515A (en) * | 2016-01-14 | 2018-08-28 | 莫门蒂夫性能材料股份有限公司 | Anti fogging coating composite and preparation method thereof |
| CN108715698A (en) * | 2018-05-23 | 2018-10-30 | 万博新材料科技（南通）有限公司 | The cured permanent super hydrophilic anti-fog coatings of UV/EB |
| CN112194775A (en) * | 2020-09-29 | 2021-01-08 | 深圳市科汇泰科技有限公司 | Water-based ultraviolet-curing polyurethane oligomer, preparation method thereof and ultraviolet-curing long-acting antifogging coating |
| JP2021004350A (en) * | 2018-10-23 | 2021-01-14 | セントラル硝子株式会社 | Antifogging article and method for producing the same |
-
2021
- 2021-03-29 CN CN202110333764.2A patent/CN113061391B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2006019175A1 (en) * | 2004-08-19 | 2008-05-08 | 関西ペイント株式会社 | Photocurable composition for antifogging film formation |
| CN101489948A (en) * | 2006-08-23 | 2009-07-22 | 中央硝子株式会社 | Non-fogging preproduction, non-fogging articles and coating fluid for the articles |
| CN101602913A (en) * | 2009-06-26 | 2009-12-16 | 广州慧谷化学有限公司 | A kind of ultraviolet light curing anti fogging coating composite and compound method thereof |
| EP3115387A1 (en) * | 2015-07-08 | 2017-01-11 | Universiteit Gent | Novel urethane based materials, derivatives, methods of their preparation and uses |
| US20180194890A1 (en) * | 2015-07-08 | 2018-07-12 | Universiteit Gent | Novel urethane based materials, derivatives, methods of their preparation and uses |
| CN108463515A (en) * | 2016-01-14 | 2018-08-28 | 莫门蒂夫性能材料股份有限公司 | Anti fogging coating composite and preparation method thereof |
| CN106118173A (en) * | 2016-07-28 | 2016-11-16 | 上海维凯光电新材料有限公司 | Hydrophilic antifogging coating composition of photo-thermal dual curable and preparation method thereof |
| CN106752857A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of the super hydrophilic antifogging coating of dual cure acrylate |
| CN107513345A (en) * | 2017-09-19 | 2017-12-26 | 上海纵港广告器材股份有限公司 | A kind of preparation method of unsaturated type polyurethane coating |
| CN108715698A (en) * | 2018-05-23 | 2018-10-30 | 万博新材料科技（南通）有限公司 | The cured permanent super hydrophilic anti-fog coatings of UV/EB |
| JP2021004350A (en) * | 2018-10-23 | 2021-01-14 | セントラル硝子株式会社 | Antifogging article and method for producing the same |
| CN112194775A (en) * | 2020-09-29 | 2021-01-08 | 深圳市科汇泰科技有限公司 | Water-based ultraviolet-curing polyurethane oligomer, preparation method thereof and ultraviolet-curing long-acting antifogging coating |
Non-Patent Citations (6)
| Title |
|---|
| SHINYA TAKAHASHI等: "Surface Dynamics for Enhanced Hydrophilic Copolymers and Their Anti-Fogging Capabilities"", 《2007北京国际粘接技术研讨会暨第二届亚洲粘接技术研讨会论文集》 * |
| TAHK,D等: "Fabrication of Antireflection and Antifogging Polymer Sheet by Partial Photo polymerization and Dry Etching", 《LANGMUIR》 * |
| XIE,BB等: "A Study on Corrosion resistance and Weatherability of Fluorocarbon Anti-corrosion Coatings for External Surface of Ocean Platform", 《ADVANCED MANUFACTURING TECHNOLOGY AND SYSTEMS》 * |
| YUNJIAO GU等: "Surface-engraved nanocomposite coatings featuring interlocked reflection-reducing, anti-fogging, and contamination-reducing performances", 《PROGRESS IN ORGANIC COATINGS》 * |
| 孔令涛: "紫外光固化亲水防雾丙烯酸酯涂层的制备及性能研究", 《中国优秀硕士学位论文全文数据库（电子期刊） 工程科技Ⅰ辑》 * |
| 王朝栋: "UV感光丙烯酸酯型水性聚氨酯的合成与应用研究", 《中国优秀硕士学位论文全文数据库（电子期刊） 工程科技Ⅰ辑》 * |
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