CN107011760B - Coating composition for antireflection coating, method of preparing the same, and antireflection film prepared therefrom - Google Patents
Coating composition for antireflection coating, method of preparing the same, and antireflection film prepared therefrom Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
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- C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
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- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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Abstract
The present invention provides a coating composition for an antireflection coating, comprising: 30 to 90 weight percent of a water soluble polymer based on total solids weight of the composition, the water soluble polymer selected from polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyethyleneimine, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, a copolymer of polyvinyl methyl ether and maleic anhydride, or a combination thereof; silica particles in an amount of 10 to 50 wt% based on the total solids weight of the composition; and a polymer emulsion having a particle diameter of 150nm or less, wherein the content of the polymer emulsion is 0 to 50% by weight based on the weight of the contained solids in the composition. The present invention also provides a method of preparing the coating composition and an antireflection film including an antireflection coating layer prepared from the coating composition.
Description
Technical Field
The invention relates to a coating composition for an antireflection coating, a preparation method thereof and an antireflection film prepared from the coating composition.
Background
Antireflective polymer films ("AR films") are becoming increasingly important. For example, to reduce the amount of light reflected by a surface, AR films are typically constructed from alternating high index of refraction ("RI") and low index of refraction polymer layers.
U.S. Pat. No. 3, 6177131, 1 discloses a solution formulation for antireflection coatings, in which the pH is greater than or equal to 7 and the constituent is silane RaSiX4-aAnd a polymer containing at least one of a hydroxyl group or an amino group.
Chinese patent CN102923966 discloses an antireflection glass coating composition and a preparation method thereof. The composition comprises a low-refractive index and high-refractive index two-part coating, wherein additives for enhancing reflection effect such as polyethylene glycol (PEG), polyvinylpyrrolidone (PVP) and the like can be added, and the dosage of the additives is 0.001-40% of the total weight of the low-refractive index sol-gel coating.
Moisture absorption is an important drawback for antireflective coatings that results in a reduction in the light transmittance of the film layer, thereby limiting its application.
Therefore, there is still a need to develop an antireflection film having improved moisture absorption properties.
Disclosure of Invention
The present inventors have unexpectedly found that by using polymer emulsion microspheres of a specific particle size in combination with a high light transmittance aqueous polymer-SiO2The particle mixed system can improve the moisture absorption performance without damaging high light transmittance and high aging resistance.
Accordingly, the present invention provides, in a first aspect, a coating composition for an antireflection coating, comprising:
30 to 90 weight percent of a water soluble polymer based on total solids weight of the composition, the water soluble polymer selected from polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyethyleneimine, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, a copolymer of polyvinyl methyl ether and maleic anhydride, or a combination thereof;
silica particles in an amount of 10 to 50 wt% based on the total solids weight of the composition; and
a polymer emulsion having a particle size of 150nm or less, wherein the polymer emulsion is contained in an amount of 0 to 50% by weight based on the weight of the contained solids in the composition.
In another aspect of the present invention, there is provided a method of preparing the aforementioned coating composition, comprising the steps of:
a) adding a water-soluble polymer to water to form an aqueous solution;
b) mixing the aqueous solution of step a) with a polymer emulsion, followed by adjusting the pH to greater than 7;
c) mixing the mixture of step b) with SiO in the form of particles2Or a mixture of silanes capable of hydrolyzing to form silica; and (c).
Optionally (c) is
d) Adjusting the pH value of the product solution obtained in step c) to less than 7, and adding a metal salt thereto.
In still another aspect of the present invention, there is provided an antireflection film comprising a substrate and an antireflection coating formed on the substrate from the coating composition of the present invention.
The antireflection film has high light transmittance, does not absorb moisture, and has high aging performance.
Drawings
Fig. 1 shows a typical structure of an antireflection film, in which a is an antireflection coating and b is a substrate, typically glass, on which the antireflection coating is coated.
Fig. 2 shows a Scanning Electron Microscope (SEM) image of a cross section of the antireflection film obtained in comparative example 1.
Fig. 3 shows a cross-sectional SEM image of the antireflection film obtained in example 1-1.
Detailed Description
For the following terms, these definitions shall be used, unless a different definition is given in the claims or elsewhere in the specification.
The term "polymer" will be understood to include polymers, copolymers (e.g., polymers formed using two or more different monomers), oligomers and combinations thereof, as well as polymers, oligomers, or copolymers that can be formed in miscible blends.
The recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g. the numerical range 1 to 10 includes 1, 1.5, 3.33, and 10).
As used in this specification and the appended claims, the singular forms "a", "an", "the", and "the" include plural referents unless the content clearly dictates otherwise. Thus, for example, a mixture containing "a compound" includes a mixture of two or more compounds. As used in this specification and the appended claims, the word "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise.
Unless otherwise indicated, all numbers expressing quantities of ingredients, performance measurements, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by those skilled in the art based upon the teachings of the present invention. And not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value must contain certain errors due to the standard deviation of the various testing methods.
As used herein, "solids content" is used to describe the portion of the coating composition of the present invention that is included in addition to water, including emulsion phase microspheres in a polymer emulsion, and also including SiO formed2Particles, and added water-soluble polymer. For example, when describing the solids content of an emulsion, an emulsion solids content of 50% refers to the weight of emulsion phase microspheres in the emulsion as a percentage of the total weight of the emulsion. Alternatively, the description "the amount of polymer emulsion is 1-50% of the total solids content of the composition, based on the solids present" means that the weight of emulsion phase microspheres in the polymer emulsion is 1-50% of the total solids content of the composition, including all solids in the composition, including emulsion phase microspheres, and also including the SiO formed2Particles, and water-soluble polymers.
Hereinafter, the present invention will be described in more detail.
One aspect of the present invention provides a coating composition for an anti-reflective coating layer, comprising:
a water-soluble polymer comprising groups that readily interact weakly with the silica particles;
silica particles; and
a polymer emulsion having a particle diameter of 150nm or less.
The water-soluble polymers useful in the present invention have good water solubility, are generally basic, and contain groups that tend to allow the silica particles to interact weakly (e.g., form hydrogen bonds). Examples of such groups include hydroxyl, amino, imino, amido, carboxylic acid, carboxylic anhydride, and ethers. Examples of water-soluble polymers useful in the present invention include, but are not limited to, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyethyleneimine, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide (e.g., oxidized polyethylene, polypropylene oxide), and a copolymer of polyvinyl methyl ether and maleic anhydride, or a combination thereof, more preferably polyvinylpyrrolidone.
In particular, the polyvinylpyrrolidones useful in the present invention may be those available from BASF under the trade name LUVITEC, and may also be PVP available from tapping peck corporation or shanghai vitamin a materials corporation.
The molecular weight of the water-soluble polymer is not particularly limited, and for example, the number average molecular weight thereof may be 10,000-400,000, preferably 50,000-300,000. The water-soluble polymer has a K value of K30-K90, preferably K40-K85, more preferably K50-K80. The K value here means a characteristic value relating to the relative viscosity of the aqueous PVP solution.
The water-soluble polymer may be present in an amount of 30 to 90 wt%, preferably 40 to 80 wt%, more preferably 50 to 70 wt%, based on the total weight of the composition. According to some embodiments, a water-soluble polymer (e.g., polyvinylpyrrolidone) may comprise the water-soluble polymer-SiO2The total weight of the particle mixing system is 50 to 90 wt%, preferably 70 to 90 wt%. Without being bound by any theory, the present inventors have found that a water-soluble polymer content in this range can optimize the light transmittance of the coating.
The silica particles typically have a particle size of less than 20nm, more preferably less than 10nm, to achieve good abrasion resistance of the coating while maintaining adequate light transmittance. The silicas suitable for use in the present invention can be commercial silica particles or generated in situ from the corresponding silane.
Silanes suitable for use in the present invention to form silica particles in situ contain hydrolyzable and condensable groups. These hydrolyzable and condensable groups form an inorganic network containing Si-O-Si units. Non-limiting examples of silanes include methyl orthosilicate (Si (OCH)3)4) Tetraethoxysilane (Si (OC)2H5)4) Propyl orthosilicate (Si (OC)3H7)4) Isopropyl n-silicate (Si [ OCH (CH) ]2)]4) Butyl silicate (Si (OC)4H9)4) Isobutyl silicate (Si [ OCH ]2CH(CH3)2]4) Methyltrimethoxysilane (CH)3Si(OCH3)3) Methyltriethoxysilane (CH)3Si(OC2H5)3) Ethyltrimethoxysilane (C)2H5Si(OCH3)3) Ethyltriethoxysilane (C)2H5Si(OC2H5)3) Vinyl trimethoxy silane (CH)2CHSi(OCH3)3) Vinyl triethoxysilane (CH)2CHSi(OC2H5)3) Isobutyl triethoxy silane ((CH)3)2CHCH2Si(OC2H5)3) Gamma-aminopropyltriethoxysilane (NH)2(CH2)3Si(OC2H5)3) Gamma-glycidoxypropyltrimethoxysilane (CH)2CH(O)CH2O(CH2)3Si(OCH3)3) Or gamma- (methacryloyloxy) propyltrimethoxysilane (CH)2＝C(CH3)COOC3H6Si(OCH3)3). Preferably, the silane is methyl orthosilicate TMOS or ethyl orthosilicate TEOS.
The silica particles may be present in the coating composition in an amount of from 10 to 50 wt%, preferably from 12 to 40 wt%, more preferably from 15 to 30 wt% of the total solids content of the coating composition.
The kind of the polymer emulsion is not particularly limited as long as the particle diameter thereof is 150nm or less. Applicants have found that as the emulsion content increases, the better the coating's moisture absorption. In some embodiments of the invention, the particle size of the polymer emulsion is preferably 120nm or less, more preferably from 10nm to 100nm, most preferably from 40 to 80 nm. The applicants have surprisingly found that coatings prepared from the coating compositions of the present invention, after addition of a polymer emulsion to the specific system of the present invention, exhibit pores having a pore size about the same as the particle size of the polymer emulsion, that the initial light transmission does not significantly decrease upon introduction of such pores, that the refractive index and light transmission of the coating can still be maintained, and that in the preferred particle size range of the emulsion described above, e.g., 10nm to 100nm, and most preferably 40-80nm, coatings having excellent light transmission and excellent moisture absorption are obtained.
Polymer emulsions suitable for use in the present invention are, for example, polyurethane emulsions, polystyrene emulsions, polyethylene-vinyl acetate emulsions, polystyrene emulsions, polyacrylic emulsions, and the like. Polyurethane emulsions, polyethylene emulsions and polyacrylic emulsions are preferred; more preferred are polystyrene emulsions and polyacrylate emulsions, such as may be obtained from BASF; under the trade name Acronal 7208. Preferably, the polymer emulsion is selected from a polystyrene emulsion or a polyacrylic emulsion.
The content of the polymer emulsion is not particularly limited. Applicants have found that the more the polymer emulsion is added, the more the moisture absorption is improved, but the more the addition is, the lower the initial light transmittance is. Thus, the polymer emulsion preferably comprises from 0 to 50%, more preferably from 10 to 20% by weight of the total solids, based on the solids present.
The coating composition of the invention may also comprise a metal salt, preferably in an amount of 0 to 60% by weight, preferably 5 to 40%, more preferably 5 to 30% by weight, based on the weight of the composition (in solids). Examples of metal salts are aluminium, zirconium or cerium salts, etc., which are advantageous for improving the ageing resistance of the coating. The counter ion of the metal salt may be an inorganic acid group such as nitrate, chloride, halide (fluoride, chloride, bromide or iodide), chlorate, arsenate; or an organic acid group such as acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, acetylacetonate, and the like.
The metal salt may be added to the coating as a metal salt stabilized by a chelating agent to improve the stability of the solution. The chelating agent may employ those conventionally used in the art, such as aminocarboxylic acids, e.g., ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), ethyleneglycol bis (2-aminoethyl ether) tetraacetic acid (EGTA), and the like. Preferred are DTPA, EDTA and HEDTA.
The present invention also provides an antireflection film having a layer formed from the coating composition of the present invention. The antireflection film has high light transmittance and aging performance and does not absorb moisture.
The coating composition of the present invention can be prepared by stirring the solution uniformly by a conventional mixing method. For example, the method of preparing the coating composition of the present invention may comprise the steps of:
a) adding a water-soluble polymer to water to form an aqueous polymer solution;
b) mixing the aqueous solution of step a) with a polymer emulsion, followed by adjusting the pH to greater than 7;
c) mixing the mixture of step b) with SiO in the form of particles2Or a mixture of silanes that can hydrolyze to form silica.
In case a metal salt is used, the method further comprises the steps of:
d) adjusting the pH value of the product solution obtained in step c) to less than 7, and adding a metal salt, such as an aluminum salt, a zirconium salt or a cerium salt, thereto.
The antireflection film can be obtained by coating the coating composition of the present invention on a substrate by a conventional coating method, followed by drying and calcination, wherein the calcination temperature may be 300 ℃ or more, preferably in the range between 600 ℃ and 900 ℃. The thickness of the coating formed is generally 50 to 200nm, preferably 70 to 150nm, more preferably 80 to 130 nm.
The substrate to which the coating composition of the present invention is applied is typically glass. In the case of single-sided coating, the glass comprising a coating made from the coating composition of the invention has a reflectivity of 4 to 6%, preferably 4 to 5%. The light transmittance is 94-96%, preferably 95-96%.
The coating composition of the invention can make the antireflection coating prepared from the coating composition have remarkably improved moisture absorption and high light transmittance. Certain embodiments may also have high aging resistance.
Examples
The advantages of the present invention are further illustrated in the following non-limiting examples. The particular materials and amounts thereof recited in the examples, as well as other experimental conditions, should not be construed to unduly limit this invention. In the present invention, parts, ratios, percentages, etc. are by mass unless otherwise specified.
Raw materials and sources:
polyvinylpyrrolidone PVP (K70) was from bopeck new materials, inc;
acrylic emulsions (45nm,80nm,110nm) with different particle sizes are from BASF company, the trade name of 45nm emulsion is Acronal 7208, the trade name of 80nm emulsion is Acronal 7209, and the trade name of 110nm emulsion is Acronal 7210;
the preparation method of the 65nm polystyrene emulsion comprises the following steps: sequentially adding 70g of deionized water, 0.91g of ammonia water, 0.018g of oleic acid, 0.158g of glycidyl methacrylate and a styrene monomer into a three-necked bottle, introducing nitrogen to remove oxygen for 1 hour, starting stirring, raising the temperature to 70 ℃, adding 80mg of potassium persulfate, and continuing stirring for 2 hours;
TEOS (tetraethyl orthosilicate) and Al (NO)3)3·9H2O, all from the national chemical reagents, Inc.;
nBuNH2(n-butylamine) and phosphoric acid, both from national chemical reagents, Inc.
Silica sol 1115(4nm, 16.4%), 2326(5nm, 15.9%), 8699(2-3nm, 15.7%), 2327(20nm, 41.7%), 2329(75nm, 52.6%), all purchased from Nalco; and
EDTA (ethylene diamine tetraacetic acid) from national Chemicals, Inc.
Comparative example: 1.6 g of PVP (K70) was dissolved in 100 g of water, the pH was adjusted to 11.0 with n-butylamine, 1.86 g of tetraethyl orthosilicate was added and the mixture was stirred overnight.
Example 1-1: 1.6 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solid content: 36.7%) was added, stirring was carried out for 3 hours, the pH was adjusted to 11.0 with n-butylamine, and then 1.86 g of tetraethyl orthosilicate was added and stirred overnight.
Example 2-1: 1.6 g of PVP (K70) was dissolved in 100 g of water, 1.01 g of a polyacrylate emulsion having a particle size of 110nm (solid content: 47.0%) was added, stirring was carried out for 3 hours, the pH was adjusted to 11.0 with n-butylamine, and then 1.86 g of tetraethyl orthosilicate was added and stirred overnight.
Example 2-2: 1.6 g of PVP (K70) was dissolved in 100 g of water, 1.01 g of a polyacrylate emulsion having a particle size of 80nm (solid content: 47.0%) was added, stirring was carried out for 3 hours, the pH was adjusted to 11.0 with n-butylamine, and then 1.86 g of tetraethyl orthosilicate was added and stirred overnight.
Examples 2 to 3: 1.6 g of PVP (K70) was dissolved in 90 g of water, 10.18 g of a 65 nm-sized polystyrene emulsion (solid content: 4.54%) was added thereto, and the mixture was stirred for 3 hours, and after adjusting the pH to 11.0 with n-butylamine, 1.86 g of tetraethyl orthosilicate was added thereto and stirred overnight.
Examples 3-1 to 3-5: 1.6 g of PVP (K70) was dissolved in 100 g of water, 0.34 g to 3.03 g (specific amount shown in Table 3 below) of an 80 nm-sized polyacrylate emulsion (solid content: 47.0%) was added, and stirred for 3 hours, and after adjusting the pH to 11.0 with n-butylamine, 1.86 g of tetraethyl orthosilicate was added and stirred overnight.
Examples 3-6 to 3-8: 1.6 g of PVP (K70) was dissolved in 90 g of water, 5.09 g to 20.36 g (specific amount shown in Table 3 below) of a 65 nm-sized polystyrene emulsion (solid content: 4.54%) was added, and stirred for 3 hours, and after adjusting the pH to 11.0 with n-butylamine, 1.86 g of tetraethyl orthosilicate was added and stirred overnight.
Example 4-1: 1.6 g of PVP (K30) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solid content: 36.7%) was added, stirring was carried out for 3 hours, the pH was adjusted to 11.0 with n-butylamine, and then 1.86 g of tetraethyl orthosilicate was added and stirred overnight.
Example 4-2: 1.6 g of PVP (K50) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solid content: 36.7%) was added, stirring was carried out for 3 hours, the pH was adjusted to 11.0 with n-butylamine, and then 1.86 g of tetraethyl orthosilicate was added and stirred overnight.
Examples 4 to 3: 1.6 g of PVP (K90) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solid content: 36.7%) was added, stirring was carried out for 3 hours, the pH was adjusted to 11.0 with n-butylamine, and then 1.86 g of tetraethyl orthosilicate was added and stirred overnight.
Example 5-1: 3.2 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a 45 nm-particle polyacrylate emulsion (solids content: 36.7%) was added, and after stirring for 3 hours, 3.44 g of 8699 (solids content: 15.7%) were added.
Example 5-2: 3.2 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a 45 nm-particle polyacrylate emulsion (solids content: 36.7%) was added, and after stirring for 3 hours, 3.29 g of 1115 (solids content: 16.4%) were added.
Examples 5 to 3: 3.2 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solids content: 36.7%) was added, and after stirring for 3 hours, 3.37 g of 2326 (solids content: 15.9%) were added.
Examples 5 to 4: 3.2 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solids content: 36.7%) was added, and after stirring for 3 hours, 1.29 g of 2327 (solids content: 41.7%) were added.
Examples 5 to 5: 3.2 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solids content: 52.6%) was added, and after stirring for 3 hours, 1.03 g of 2329 (solids content: 15.7%) was added.
Example 6-1: 0.8 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solid content: 36.7%) was added, stirring was carried out for 3 hours, the pH was adjusted to 11.0 with n-butylamine, and then 1.86 g of tetraethyl orthosilicate was added and stirred overnight.
Example 6-2: 3.2 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solid content: 36.7%) was added, stirring was carried out for 3 hours, the pH was adjusted to 11.0 with n-butylamine, and then 1.86 g of tetraethyl orthosilicate was added and stirred overnight.
Examples 6 to 3: 1.2 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solids content: 36.7%) was added, and after stirring for 3 hours, 4.88 g of 1115 (solids content: 16.4%) were added.
Examples 6 to 4: 1.6 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a 45 nm-particle polyacrylate emulsion (solids content: 36.7%) was added, and after stirring for 3 hours, 3.29 g of 1115 (solids content: 16.4%) were added.
Example 7-1: 1.6 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solid content: 36.7%) was added, stirring was carried out for 3 hours, after the pH was adjusted to 11.0 with n-butylamine, 1.86 g of tetraethyl orthosilicate was added and stirring was carried out overnight, and thereafter 1.04 g of a 20% aqueous solution of aluminum nitrate nonahydrate was added.
Example 7-2: 0.416 g of ethylenediaminetetraacetic acid was added to 100 g of water, the pH value was adjusted to 11.2 with n-butylamine, the solution was stirred until it became clear, 1.04 g of a 20% aqueous solution of aluminum nitrate nonahydrate were added, 1.6 g of PVP (K70) and 1.26 g of a polyacrylate emulsion having a particle size of 45nm (solid content: 36.7%) were then added, the mixture was stirred for 3 hours, 1.86 g of tetraethyl orthosilicate was added and the mixture was stirred overnight.
Examples 7 to 3: 1.6 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion (solid content: 36.7%) having a particle size of 45nm was added, stirring was carried out for 3 hours, the pH was adjusted to 11.0 with n-butylamine, 1.86 g of tetraethyl orthosilicate was added and stirred overnight, the solution was stored at 60 ℃ for 2 days, then phosphoric acid was added to adjust the pH to 2.5, and thereafter 1.04 g of a 20% aqueous solution of aluminum nitrate nonahydrate was added.
Examples 7 to 4: 1.6 g of PVP (K70) was dissolved in 100 g of water, 1.26 g of a polyacrylate emulsion (solid content: 36.7%) having a particle size of 45nm was added, stirring was carried out for 3 hours, the pH was adjusted to 11.0 with n-butylamine, 1.86 g of tetraethyl orthosilicate was added and stirred overnight, the solution was stored at 60 ℃ for 2 days, then phosphoric acid was added to adjust the pH to 2.5, and thereafter 2.08 g of a 20% aqueous solution of aluminum nitrate nonahydrate was added.
The coatings prepared by the above examples and comparative examples were prepared into coatings by the following methods, and their respective properties were measured.
Experiment and measurement:
preparing an antireflection coating:
the glass for coating is from the letter glass company Limited, and before use, the glass is washed by deionized water and dried at 120 ℃.
The film is prepared by dip coating, the used instrument is a KSV dip coating instrument, glass is placed in solution statically during film coating, the solution is kept for 15 seconds, then the solution is pulled out at different speeds, the solution on the back surface is wiped clean and then dried for 5 minutes at 120 ℃, then calcined at 750 ℃ for 2 minutes and cooled to room temperature in air, and finally the film shown in figure 1 is obtained.
And (3) particle size testing:
the apparatus used was Zetasizer Nano-ZS (ZEN 3600), and the particle sizes mentioned were all Z-average particle sizes.
And (3) transmission spectrum testing:
BYK data were obtained with a BYK instrument in the wavelength range of 380-780 nm.
Lambda data were obtained from a Lambda 1050Perkin-Elmer spectrometer with a wavelength range of 380-1100 nm.
And (3) aging test:
salt spray aging test: 5% aqueous NaCl solution was sprayed at 35 ℃ for 96 hours (IEC 61701). After the salt spray test, the film was rubbed with cotton cloth using a 1 kg load for 5 times to see the film detachment.
Pressure cooker boil test (PCT): boiling with water vapor at 120 deg.C and 2atm for 48 hr.
And (3) wear resistance test:
the apparatus used was CM-5M238BB from SDLAtlas under a load of 1 kg, and the film was rubbed with cotton cloth 20 times to see the peeling of the film.
Moisture absorption test:
the film was placed in an environment of 25 ℃ and 90% humidity, and allowed to stand for 24 hours to conduct a light transmittance test.
Action of the Polymer emulsion
TABLE 1 light transmittance (BYK data) and refractive index of coatings corresponding to different formulations before and after moisture absorption
As can be seen from Table 1, the coating obtained without the addition of the polymer emulsion in the comparative example had very small pores (FIG. 2) and had a refractive index of about 1.34, and although the initial light transmittance was high, the refractive index rose to about 1.37 due to moisture absorption after being left at room temperature for 1 day at 80% humidity, and the light transmittance decreased by as much as 1.3%. In contrast, in example 1-1, after the addition of the appropriate polymer emulsion, the obtained coating had pores with a size of about the particle size of the polymer emulsion (fig. 3), the initial light transmittance was not decreased compared to that without the addition of the polymer emulsion, and the refractive index and light transmittance did not change significantly after one day of standing, indicating that the moisture absorption performance of the coating was greatly improved.
Particle size of Polymer emulsion
TABLE 2 light transmittance (BYK data) and refractive index of coatings corresponding to polymer emulsions of different particle sizes before and after moisture absorption
As can be seen from Table 2, the addition of the polymer emulsion significantly improves the moisture absorption properties regardless of the polymer emulsion. However, if the particle size of the polymer emulsion is less than 100nm, preferably 40 to 80nm, a high light transmittance coating is more easily obtained.
Amount of Polymer emulsion
TABLE 3 light transmittance (BYK data) and refractive index of coatings before and after moisture absorption for varying amounts of polymer emulsion
As can be seen from Table 3, the more the polymer emulsion was added, the more the improvement in moisture absorption properties was observed, but the more the addition was made, the adverse effect on the initial light transmittance was caused. In combination, the amount of polymer emulsion (solids content) is preferably from 1 to 50%, preferably from 10 to 20%, based on the total solids content.
Molecular weight of polyvinylpyrrolidone added:
TABLE 4 permeability enhancement values (BYK data) for films from solutions of different molecular weights of polyvinylpyrrolidone
| Examples | PVP | ΔT％ |
| Comparative test | \ | 1.0 |
| Example 4-1 | K30 | 2.3 |
| Example 4 to 2 | K50 | 2.6 |
| Examples 1 to 1 | K70 | 3.0 |
| Examples 4 to 3 | K90 | 2.1 |
As can be seen from Table 4, the examples using polyvinylpyrrolidone of different molecular weights all achieved significant permeability enhancement (increase in light transmittance), with the highest permeability enhancement of examples 1-1 using polyvinylpyrrolidone of K70.
Particle size of silica particles:
TABLE 5 anti-reflection value of the corresponding film layer of the solutions obtained from silica sols of different particle sizes
As can be seen from Table 5, the silica selected for its particle size of 75nm had a lower permeability than the remaining examples, while having a general abrasion resistance. Therefore, in order to ensure that the resulting film layer has good abrasion resistance and light transmittance, silica having a particle size of less than 20nm, more preferably less than 10nm, is preferable.
Ratio of polyvinylpyrrolidone to silica:
TABLE 6 light transmittance of corresponding films of solutions of different PVP (K70) and silica ratios
As can be seen from Table 3, PVP/(PVP + SiO) when TEOS and 1115 are converted to silica2) The value of (A) is preferably 50 to 95%, more preferably 60 to 90%, so that higher light transmittance is obtained.
Addition and amount of Metal salt
TABLE 7 influence of different aluminum salt additions on solution viscosity and stability and light transmittance of the corresponding coatings
TABLE 8 Effect of different aluminum salt additions on the aging behavior of the corresponding coatings
As can be seen from tables 7 and 8, although all of the examples give high light transmittance and low moisture absorption, the aging resistance can be improved by properly adding an aluminum salt (examples 7-2 to 7-4). However, since the solution was a basic solution, the direct addition of aluminum salt resulted in the formation of a large amount of precipitates (example 7-1), and if the aluminum salt was stabilized with a chelate compound such as EDTA, the stability of the solution could be improved to some extent, but the fogging could still be observed on the corresponding film layer (example 7-2), and the final light transmittance was inferior to that of example 1-1 and examples 7-3 and 7-4. In examples 7-3 and 7-4, the solution was acidified and then aluminum salt was added, and the resulting solution had good stability, good light transmittance of the corresponding film layer, and good aging properties.
In summary, the present invention can be described as follows:
1. a coating composition for an antireflective coating comprising:
30 to 90 weight percent of a water soluble polymer based on total solids weight of the composition, the water soluble polymer selected from polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyethyleneimine, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, a copolymer of polyvinyl methyl ether and maleic anhydride, or a combination thereof;
silica particles in an amount of 10 to 50 wt% based on the total solids weight of the composition; and
a polymer emulsion having a particle size of 150nm or less, wherein the polymer emulsion is contained in an amount of 0 to 50% by weight based on the weight of the contained solids in the composition.
2. The coating composition according to item 1, wherein the polymer emulsion has a particle size of 120nm or less.
3. The coating composition according to item 1, wherein the polymer emulsion has a particle size of 10 to 100 nm.
4. The coating composition according to item 1, wherein the particle size of the polymer emulsion is 40 to 80 nm.
5. The coating composition according to item 1, wherein the polymer emulsion is contained in an amount of 10 to 20% by weight of the total solids in the composition, based on the contained solids.
6. The coating composition according to item 1, wherein the silica particles are generated in situ from the corresponding silane, which contains hydrolysable and/or condensable groups.
7. The coating composition of item 1, wherein the water soluble polymer is polyvinylpyrrolidone.
8. The coating composition according to item 7, wherein the polyvinylpyrrolidone has a number average molecular weight of 10,000-400,000, preferably 50,000-300,000.
9. The coating composition according to item 7, wherein the polyvinylpyrrolidone comprises 50 to 95 wt%, preferably 60 to 90 wt% of the total weight of the water-soluble polymer and the silica particles.
10. The coating composition according to item 1, wherein the water-soluble polymer is present in an amount of 40 to 80 wt%, preferably 50 to 70 wt%, based on the total solids weight of the composition.
11. The coating composition according to item 1, wherein the silica particles have a particle size of less than 20nm, preferably less than 10 nm.
12. The coating composition of item 1, further comprising 0-60 wt% of a metal salt selected from an aluminum salt, a zirconium salt, a cerium salt, or a combination thereof, based on the total solids weight of the composition.
13. The coating composition of item 1, wherein the polymer emulsion is selected from a polystyrene emulsion or a polyacrylic emulsion.
14. A method of making the coating composition of any one of the preceding claims, comprising the steps of:
a) adding a water-soluble polymer to water to form an aqueous solution;
b) mixing the aqueous solution of step a) with a polymer emulsion followed by adjusting the pH to greater than about 7;
c) mixing the mixture of step b) with SiO in the form of particles2Or a mixture of silanes capable of hydrolyzing to form silica; and (c).
Optionally (c) is
d) Adjusting the pH value of the product solution obtained in step c) to less than 7, and adding a metal salt thereto.
15. An antireflection film comprising a substrate and an antireflection coating formed on the substrate from the coating composition of any one of items 1 to 13.
While the invention has been described in terms of preferred embodiments, it will be understood, of course, that the invention is not limited thereto since modifications may be made by those skilled in the art, particularly in light of the foregoing teachings.
Claims (17)
1. A coating composition for an antireflective coating comprising a mixture comprising:
30 to 90 weight percent of a water soluble polymer based on total solids weight of the composition, the water soluble polymer selected from polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyethyleneimine, hydroxyethylcellulose, polyalkylene oxide, a copolymer of polyvinyl methyl ether and maleic anhydride, or a combination thereof;
silica particles in an amount of 10 to 50 wt% based on the total solids weight of the composition; and
a polymer emulsion having a particle size of 150nm or less, wherein the polymer emulsion is contained in an amount of 0.34 to 50% by weight based on the weight of the total solids in the composition,
wherein the polymer emulsion is selected from polyurethane emulsion, polyethylene-vinyl acetate emulsion, polystyrene emulsion or polyacrylic emulsion, and
the total solids weight of the components in the coating composition is less than or equal to 100 wt%.
2. The coating composition of claim 1, wherein the polymer emulsion is a polystyrene emulsion.
3. The coating composition according to claim 1 or 2, wherein the particle size of the polymer emulsion is 120nm or less.
4. The coating composition according to claim 1 or 2, wherein the particle size of the polymer emulsion is 10-100 nm.
5. The coating composition according to claim 1 or 2, wherein the particle size of the polymer emulsion is 40-80 nm.
6. The coating composition of claim 1 or 2, wherein the polymer emulsion is present in an amount of 10 to 20% by weight of the total solids in the composition, based on the solids present.
7. A coating composition according to claim 1 or 2, wherein the silica particles are generated in situ from the corresponding silane containing hydrolysable and/or condensable groups.
8. The coating composition of claim 1 or 2, wherein the water soluble polymer is polyvinylpyrrolidone.
9. The coating composition of claim 8, wherein the polyvinylpyrrolidone has a number average molecular weight of 10,000-400,000.
10. The coating composition of claim 8, wherein the polyvinylpyrrolidone has a number average molecular weight of 50,000-300,000.
11. The coating composition of claim 8, wherein the polyvinylpyrrolidone comprises 50 to 90 wt% of the total weight of the water-soluble polymer and the silica particles.
12. The coating composition of claim 1 or 2, wherein the water soluble polymer is present in an amount of 50 to 70 wt% based on the total solids weight of the composition.
13. The coating composition according to claim 1 or 2, wherein the silica particles have a particle size of less than 20 nm.
14. The coating composition of claim 1 or 2, further comprising 0-60 wt% of a metal salt selected from an aluminum salt, a zirconium salt, a cerium salt, or a combination thereof, based on the total solids weight of the composition.
15. The coating composition of claim 1, wherein the polymer emulsion is selected from a polystyrene emulsion or a polyacrylic emulsion.
16. A method of preparing the coating composition of any one of the preceding claims, comprising the steps of:
a) adding a water-soluble polymer to water to form an aqueous solution;
b) mixing the aqueous solution of step a) with a polymer emulsion, followed by adjusting the pH to greater than 7;
c) mixing the mixture of step b) with SiO in the form of particles2Mixing, or mixing the mixture of step b) with a silane capable of hydrolyzing to produce silica, said silane being hydrolyzed to produce silica particles; and the combination of (a) and (b),
optionally (c) is
d) Adjusting the pH value of the product solution obtained in step c) to less than 7, and adding a metal salt thereto.
17. An antireflection film comprising a substrate and an antireflection coating formed on the substrate from the coating composition of any of claims 1 to 15.
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