CN112094422A - High-light-transmittance barrier film and application thereof - Google Patents

High-light-transmittance barrier film and application thereof Download PDF

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CN112094422A
CN112094422A CN202010761563.8A CN202010761563A CN112094422A CN 112094422 A CN112094422 A CN 112094422A CN 202010761563 A CN202010761563 A CN 202010761563A CN 112094422 A CN112094422 A CN 112094422A
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refractive index
index layer
acid
barrier film
coating
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CN112094422B (en
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刘军虎
纪雪梅
郑燕
陈帅
刘贤豪
臧立恒
程媛
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China Lucky Group Corp
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China Lucky Group Corp
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B05D3/144—Pretreatment of polymeric substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/061—Special surface effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • 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
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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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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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
    • 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
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
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    • 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
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2433/00—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
    • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Abstract

The invention discloses a high light transmission barrier film and application thereof, wherein the structure of the barrier film sequentially comprises a substrate, a high refractive index layer and a low refractive index layer; the high refractive index layer is composed of high refractive index particles, nano oxides, phosphorus-containing compounds and acid catalysts, and the low refractive index layer is composed of carboxyl-containing polymers, hydroxyl-containing water-soluble polymers, coupling agents with groups capable of reacting with carboxyl, hydrolysis condensation products of silicon alkoxide and resin crosslinking agents. The high refractive index layer and the low refractive index layer prepared by the invention have synergistic effect, so that the light transmission performance of the base material in a visible light wave band is improved by 2-5%, and the water resistance performance of the base material is improved by 10-1000 times. The barrier film prepared by the invention can be applied to the fields of food packaging, medicine packaging, flexible packaging of photoelectric devices and the like.

Description

High-light-transmittance barrier film and application thereof
The technical field is as follows:
the invention relates to the technical field of films, in particular to a barrier film with high light transmittance.
Background art:
the barrier film material refers to a film material product with excellent gas barrier property and water vapor barrier property. The barrier film material is mainly used for preventing oxygen and water vapor from entering food and medicine packages to prevent the food and the medicine from deteriorating. With the development of electronic products, many electronic products use active metals, and in order to avoid the electronic products from deteriorating due to contact with oxygen and water vapor, barrier films are beginning to be applied to electronic products, and the requirements for barrier properties, especially water vapor barrier properties, are also increasing. For example, the WVTR of the packaging material of the general electronic product is less than 1g/m2D, WVTR of the solar cell encapsulating material is 10 or less-4g/m2D, WVTR of the OLED packaging material is less than or equal to 10-6g/m2.d。
However, the popularization of barrier film material products in the application field of electronic products requires not only ultra-high barrier properties but also excellent light transmission properties. For example, the light transmittance of the conventional glass for packaging the solar cell module can reach more than 95%, and the photoelectric conversion efficiency of the solar cell can be greatly improved due to high light transmission performance. At present, the high barrier packaging film material mainly realizes the high barrier performance of a product by depositing an inorganic oxide layer on a substrate through vacuum coating technologies such as vacuum evaporation, sputtering, chemical vapor deposition and the like, although the high barrier packaging film material has excellent flexibility compared with a glass packaging material, the high barrier packaging film material needs to deposit a thicker inorganic oxide to realize the purpose of high barrier, and the light transmittance of the barrier film is inevitably influenced, so that the application of the barrier film material in the field of electronic packaging is influenced.
The organic-inorganic hybrid high-barrier membrane disclosed in Chinese patent CN201410054673.5 is prepared by plating SiO by PECVD (plasma enhanced chemical vapor deposition) coating technologyxCyA barrier film material. The technology achieves a barrier film material with good barrier property and flexibility by controlling the proportion of organic components and inorganic components among layers, but the technology needs to continuously plate for 15 times, the thickness of the barrier layer reaches 1.4 microns, simultaneously, the outermost layer also needs to deposit alumina with the thickness of 30nm as a repairing layer by utilizing an atomic deposition technology, and the WVTR of the prepared barrier film is 8.4 multiplied by 10-5g/m2D, but the light transmittance is obviously reduced along with the increase of the number of the coating layers in the coating process, and finally, the light transmittance of a visible light waveband is only about 85 percent.
In conclusion, a high-barrier film material with high light transmission performance is developed, and has an extremely important role in popularization and application in the field of electronic packaging.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a high light transmission barrier film, which is structurally composed of a base film, a high refractive index layer and a low refractive index layer; the synergistic effect of the high refractive index layer and the low refractive index layer can obviously improve the barrier property of the base material, and can also effectively improve the light transmission property of the base material.
The technical scheme for solving the problems is as follows:
a high light transmission barrier film structurally comprises a base material, a high refractive index layer and a low refractive index layer in sequence; the high-refractive-index layer comprises the following components in parts by weight:
1 to 50 parts of particles having a high refractive index,
3 to 100 parts of nano-oxide,
0.5 to 50% of a phosphorus-containing compound,
0.5-70% of an acid catalyst;
the low refractive index layer comprises the following components in parts by weight:
4 to 200 of a carboxyl group-containing polymer,
1 to 100 parts of a water-soluble polymer containing hydroxyl groups,
0.01 to 20 parts of a coupling agent having a group reactive with a carboxyl group,
0.3 to 80 parts by mass of a hydrolytic condensation product of a silicon alkoxide,
0.015-20 parts of resin cross-linking agent.
In the high light transmission barrier film, the refractive index of the high refractive index layer is 1.5-2.0, and the thickness is 0.01-2 μm; the low refractive index layer has a refractive index of 1.3-1.5 and a thickness of 0.2-10 μm; the thickness ratio of the high refractive index layer to the low refractive index layer is 1/20-10/1.
In the barrier film having high light transmittance, the high refractive index particles in the high refractive index layer are a compound (L) having a characteristic group capable of hydrolysis bonded thereto, and the compound (L) has a general formula of MXmWherein M is one element of Ti, Zr, Zn, Mg or Ca, X is one element of methoxy, ethoxy, isopropoxy, n-butoxy, acetylacetone, carboxyl, nitro, F, Cl, Br or I, and M is a positive integer of 1-4.
In the high-light-transmittance barrier film, the nano oxide in the high-refractive-index layer is one or two of nano aluminum oxide and nano silicon oxide, and the particle size is 10 nm-200 nm.
In the barrier film having high light transmittance, the amount (n) of the substance of the M element in the high refractive index particles in the high refractive index layer3) With the amount of metal element in the nano-oxide (n)2) N is not less than 0.013/n2≤3.5。
In the barrier film with high light transmittance, the phosphorus-containing compound in the high refractive index layer comprises one or more of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, nitrilotris (methylenephosphonic acid) or N, N, N, N, -ethylenediamine tetra (methylenephosphonic acid).
The barrier film with high light transmittance contains phosphorus element (n)1) And the amount of metal element substances (n) in the nano oxide2) And the amount of M element (n) in the high-refractive-index particles3) N is more than or equal to 0.11/(n2+n3)≤2.5。
In the barrier film with high light transmittance, the acid catalyst comprises one or more of nitric acid, hydrochloric acid, sulfuric acid, boric acid, formic acid, acetic acid, butyric acid, trifluoroacetic acid, citric acid, tartaric acid, lactic acid, oxalic acid or maleic acid.
The high light transmittance barrier film is characterized in that the polymer containing carboxyl is one of polyacrylic acid, polymethacrylic acid and poly (acrylic acid/methacrylic acid) copolymer, and the molecular weight is controlled within the range of 3000-1500,000.
The water-soluble polymer containing hydroxyl is one of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, polysaccharide, chitosan or cellulose, the polymerization degree is controlled to be 500-3000, and the alcoholysis degree is controlled to be 80-99.99%.
The coupling agent with the carboxyl-reactive group is a coupling agent with amino, mercapto and epoxy groups, and is selected from one or more of gamma-aminopropyltrimethoxysilane (KH540), gamma-aminopropyltriethoxysilane (KH550), diethylaminomethyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH792), gamma-mercaptopropyltrimethoxysilane (KH590), gamma-mercaptopropyltriethoxysilane (KH580), gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane or gamma- (2, 3-epoxypropoxy) propyltriethoxysilane.
In the high light transmittance barrier film, the silicon alkoxide in the silicon alkoxide hydrolysis condensate is one or more of tetramethoxysilane, tetraethoxysilane, trimethoxyaluminum, n-propyltrimethoxysilane, methyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane and 1,3, 5-tris (3-trimethoxysilylpropyl) isocyanurate.
In the barrier film with high light transmittance, the resin crosslinking agent is one or more of zinc acetate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium polyacetylacetonate, polyhydroxy titanium stearate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate or zirconium acetate.
Advantageous effects
Compared with the prior art, the invention has the following advantages:
1. the invention controls the refractive index of the coating liquid by controlling the adding proportion of each component in the two coating liquids, thereby improving the light transmittance of different types of base materials by 2-5%.
2. According to the invention, the high refractive index layer and the low refractive index layer are matched for use, and the anti-reflection-barrier coating is formed after the coating and the curing are sequentially carried out on the base material, so that the water resistance of the base material can be improved by 10-1000 times, particularly, the base material deposited with the inorganic barrier layer can also protect the deposited layer, and meanwhile, the wear resistance and the twisting resistance of the deposited layer are improved.
3. The high refractive index layer and the low refractive index layer are aqueous coating liquid, so that the coating is safe and environment-friendly, and the prepared anti-reflection-barrier coating is simple in process and convenient for large-scale production.
Drawings
FIG. 1 is a schematic view of the structure of a barrier film of the present invention.
In the drawings, the reference numerals denote: 1-substrate, 2-high refractive index layer, 3-low refractive index layer.
Detailed Description
The invention is further illustrated with reference to specific embodiments below.
The high light transmission barrier film comprises a base material (1), a high refractive index layer (2) and a low refractive index layer (3). The high refractive index layer and the low refractive index layer are matched to form a functional layer with anti-reflection and barrier properties, so that the light transmission performance of the base material is improved, and the barrier property of the base material is effectively improved.
The invention can improve the light transmission performance of the base material in visible light by 2-5 percent and improve the water resistance performance by 10-1000 times.
High refractive index layer
It is known that light propagating on the interface of two media undergoes refraction and reflection simultaneously, and the magnitude of the light reflectivity is determined by the refractive indexes of the sample and the external transparent medium. According to the law of refraction of light, when a light ray propagates from a high refractive index medium (optically dense medium) to a low refractive index medium (optically sparse medium), the angle of refraction increases. At higher angles of incidence, total reflection may occur, so that the light is locked longer inside the high refractive index medium to form a "pool". The anti-reflection effect of the high refractive index layer and the low refractive index layer is realized according to the principle, when incident light rays are reflected from the surface of the base material and then sequentially pass through the high refractive index layer and the low refractive index layer, the light rays can form total reflection between the interfaces of the two coatings, namely, the optical cell effect, so that the effects of reducing the reflectivity of the base material and improving the light transmittance of the base material are achieved.
The high-refractive-index layer comprises the following components in parts by weight: 1-50 parts of high-refractive-index particles, 3-100 parts of nano oxides, 0.5-50 parts of phosphorus-containing compounds and 0.5-70 parts of acid catalysts.
The preparation process of the formula comprises the following steps: firstly, uniformly mixing the nano oxide, the high-refractive-index particles and water for 10 to 30 minutes to obtain uniform dispersion liquid; and then adding an acid catalyst into the dispersion liquid for activation treatment for 1 to 3 hours, finally adding a phosphorus-containing compound into the dispersion liquid, stirring at a high speed for 30 to 2 hours, and adding a mixed solvent of water and alcohol to dilute to a solid content of 5 to 30 percent, thereby obtaining the coating liquid of the high-refractive-index layer.
The nano oxide used in the invention is one or two of nano alumina dispersion liquid and nano silicon oxide dispersion liquid, and the particle size is 10 nm-200 nm. The nano oxide may be a commercially available product, or may be prepared by a known sol-gel method using an aluminum alkoxide or a silicon alkoxide under acidic conditions. The aluminum alkoxide or silicon alkoxide specifically comprises one or more of trimethoxy aluminum, triethoxy aluminum, tri-n-propoxide aluminum, triisopropoxide aluminum, tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, tetramethoxy silane, tetraethoxy silane, tetra-n-propoxyl silane, tetraisopropoxy silane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane. In the invention, silicon element in the nano silicon oxide is also used as metal element.
The solid content of the nano oxide dispersion liquid is preferably 1-15%, more preferably 2.5-10.0%; if the solid content of the dispersion liquid of the nano oxide is too low, the film forming property of the coating liquid formed by the reaction with the phosphorus-containing compound is poor, so that the barrier property of the gas barrier film is reduced; if the solid content of the dispersion liquid of the nano oxide is too high, the viscosity of the dispersion liquid increases, the dispersibility becomes poor, the reaction with the phosphorus-containing compound is not facilitated, and the barrier property of the gas barrier film is also reduced.
The high refractive index particles used in the present invention are compounds (L) containing a metal atom (M) bonded with a hydrolyzable characteristic group, and the general formula of the compounds (L) is MXmThe metal atom (M) is one element of Ti, Zr, Zn, Mg and Ca, X is one element of methoxyl, ethoxyl, isopropoxy, n-butoxy, radical, acetate, nitryl, F, Cl, Br and I, and M is a positive integer of 1-4. Specifically, the titanium compound includes tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, titanium acetylacetonate, tetraethoxyzirconium, tetraisopropoxyzirconium, n-butoxyzirconium, zirconium acetylacetonate, titanium tetrachloride, zinc chloride, zinc nitrate, zinc acetate, magnesium acetate, calcium acetate, and the like. The refractive index of the high refractive index particles is 1.50-2.60.
The phosphorus-containing compound used in the invention specifically comprises one or more of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, nitrilotris (methylenephosphonic acid), N, N, -ethylenediamine tetra (methylenephosphonic acid).
The high-refractive-index layer of the invention utilizes the chelation reaction between the nano oxide and the phosphorus-containing compound to form a firm 'metal-oxygen-phosphorus' chemical bond so as to form a compact coating, thereby achieving the purpose of barrier property. Therefore, the invention controls the reaction degree by controlling the adding proportion of the phosphorus-containing compound, and achieves the improvement of the barrier property of the coating and the light transmission property. The amount of P element substance (n) in the phosphorus-containing compound1) And the amount of metal element substances (n) in the nano oxide2) And the amount of the metal element (n) in the high-refractive-index particles3) N is more than or equal to 0.11/(n2+n3) N is not more than 2.5, more preferably not less than 0.151/(n2+n3)≤2.0；n1/(n2+n3) If the hydroxyl content of the coating is too high, the water resistance of the coating is deteriorated; n is1/(n2+n3) If the molar ratio is too low, the film formation of the coating layer is deteriorated, and the coating layer is cracked, whereby the barrier property is also deteriorated and the light transmittance is deteriorated.
The addition ratio of the high-refractive-index particles and the nano oxide in the high-refractive-index layer is a key factor for regulating and controlling the refractive index of the high-refractive-index coating. Generally, the amount of metal element (n) in the high refractive index particles is required3) With the amount of metal element in the nano-oxide (n)2) N is not less than 0.013/n23.5 or less, more preferably 0.1 or less n3/n2≤2.0；n3/n2Too high a level results in poor film formation of the coating, affecting the barrier and light transmission properties of the coating, n3/n2If the refractive index is too low, the change of the refractive index of the coating is not obvious, and the anti-reflection effect cannot be realized.
The refractive index of the high-refractive-index layer is preferably 1.5-2.0, the refractive index of the high-refractive-index coating is determined by the base material of the barrier film, the refractive index is generally required to be 0.2-0.5 higher than that of the base material, the refractive index difference between the high-refractive-index coating and the base material is not easy to be too large, interference fringes can appear on the surface of the coating to influence light transmission, and the anti-reflection effect cannot be realized if the refractive index difference is too small.
Low refractive index layer
The low refractive index layer comprises the following components in parts by weight: 4-200 parts of carboxyl-containing polymer, 1-100 parts of hydroxyl-containing water-soluble polymer, 0.01-20 parts of coupling agent with carboxyl reactive groups, 0.3-80 parts of hydrolysis condensation product of silicon alkoxide and 0.015-20 parts of resin crosslinking agent.
The specific preparation process of the low refractive index layer comprises the following steps: firstly, adding a carboxyl-containing polymer, a coupling agent with a carboxyl reactive group and a hydroxyl-containing water-soluble polymer into a reaction container in sequence, and stirring at a high speed for 0.5 to 3 hours at a temperature of between 50 and 95 ℃; then stirring the silicon alkoxide and the resin cross-linking agent in a mixed solvent of water and alcohol at a high speed for 1 to 3 hours at normal temperature to obtain a mixed liquid of a silicon alkoxide hydrolysis condensation product and the resin cross-linking agent; and finally, mixing the ester cross-linked and modified poly propionic acid with the mixed solution in proportion, stirring for 0.5-1 hour at normal temperature, and adding a mixed solvent of water and alcohol to dilute to a solid content of 5-30% to obtain the coating liquid of the low-refractive-index layer.
The carboxyl-containing polymer is one of polyacrylic acid, polymethacrylic acid and poly (acrylic acid/methacrylic acid) copolymer, and the molecular weight is preferably 3000-1500,000, more preferably 5000-500,000. When the molecular weight is too low, the gas barrier property and impact resistance of the coating layer are lowered, and when the molecular weight is too high, the solubility of the polymer in water is lowered, and when the molecular weight is too high, the ester crosslinking reaction with the water-soluble polymer containing a hydroxyl group is not facilitated.
The hydroxyl group-containing water-soluble polymer in the present invention is preferably one of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, polysaccharides, chitosan, and cellulose, and more preferably polyvinyl alcohol and ethylene-vinyl alcohol copolymer; the polymerization degree is controlled to be 500-3000, and the alcoholysis degree is controlled to be 80-99.99%. Wherein the weight ratio of the hydroxyl-containing polymer to the carboxyl-containing polymer is preferably 1/20-1/2, more preferably 1/10-1/4; when the amount of the hydroxyl group-containing polymer added is too small, crosslinking with the carboxyl group-containing polymer becomes insufficient, and the gas barrier properties of the coating layer are deteriorated, and when the amount of the hydroxyl group-containing polymer added is too large, the solubility of the carboxyl group-containing polymer modified by ester crosslinking in a solvent is deteriorated, and the gas barrier properties of the coating layer are also deteriorated.
The coupling agent with the carboxyl-reactive group reacts with the carboxyl in the carboxyl-containing polymer by utilizing the carboxyl-reactive group carried by the coupling agent and plays a role of a bridge for promoting the cross-linking reaction of the carboxyl-containing polymer and the water-soluble polymer containing the hydroxyl. The coupling agent with carboxyl reactive groups refers to a coupling agent with amino, sulfydryl and epoxy groups, and specifically comprises one or more of gamma-aminopropyltrimethoxysilane (KH540), gamma-aminopropyltriethoxysilane (KH550), diethylaminomethyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH792), gamma-mercaptopropyltrimethoxysilane (KH590), gamma-mercaptopropyltriethoxysilane (KH580), gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltriethoxysilane and aminotrimethylene phosphonic acid.
The addition amount of the coupling agent with the carboxyl-reactive group is 0.1-10% of the molar amount of the carboxyl in the carboxyl-containing polymer, the ester crosslinking between the two polymers cannot be promoted if the addition amount is too small, and the reaction degree with the carboxyl is too high if the addition amount is too large, so that the compatibility of the polymer is poor and precipitates are generated.
The hydrolysis-condensation product of silicon alkoxide in the present invention is obtained by hydrolysis-condensation of silicon alkoxide under acidic condition by sol-gel method. The general formula of the silicon alkoxide is Si (OR)4Wherein R is one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. The method specifically comprises the following steps: one or more of tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane.
The silicon alkoxide hydrolysis condensation compound is mainly used for carrying out inorganic hybrid modification on a polymer, and improving the barrier property and the humidity resistance of a polymer coating. Generally, the weight ratio of the silicon alkoxide hydrolysis condensate to the carboxyl-containing polymer is required to be 1/40-4/1, when the adding amount of the silicon alkoxide hydrolysis condensate is too small, the hybridization modification of the carboxyl-containing polymer is incomplete, the compactness and the impact resistance of a coating are reduced, and when the adding amount of the silicon alkoxide hydrolysis condensate is too large, the wettability of the low-refractive-index coating is reduced, and the film-forming property is poor.
The resin cross-linking agent in the invention is a cross-linking agent containing metal ions, and specifically comprises one or more of zinc acetate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium polyacetylacetonate, polyhydroxy titanium stearate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate and zirconium acetate.
According to the invention, the resin cross-linking agent is added in the preparation process of the silicon alkoxide hydrolysis condensation compound, and the polymer is modified after activation treatment under an acidic condition, so that on one hand, the cross-linking property and compactness of a polymer coating are improved, and on the other hand, the characteristic of high refractive index of metal ions of the resin cross-linking agent is utilized, and the control of the refractive index of the coating is realized by controlling the addition proportion of the resin cross-linking agent. The addition amount of the resin cross-linking agent in the low refractive index layer is referenced to silicon alkoxide in the silicon alkoxide hydrolysis condensation product, and the mass ratio of the resin cross-linking agent to the silicon alkoxide is preferably 1/150-1/2, and more preferably 1/100-1/4; if the addition amount of the resin crosslinking agent is too large, the stability of the coating liquid of the prepared low-refractive-index layer is deteriorated, so that the barrier property and the light transmittance of the low-refractive-index layer are deteriorated; if the amount of the resin crosslinking agent added is too low, the polymer coating is not crosslinked completely, and the barrier property of the coating is deteriorated.
The refractive index of the low-refractive-index coating prepared by the method is preferably 1.3-1.5, the refractive index of the low-refractive-index coating is determined by taking the refractive index of the high-refractive-index coating as a reference, the refractive index is generally required to be 0.1-0.5 lower than that of the high-refractive-index coating, the light transmittance performance is affected if the difference between the refractive indexes of the two coatings is too large, and the anti-reflection effect cannot be achieved if the difference between the refractive indexes of the two coatings is too small.
In the invention, the low refractive index layer and the high refractive index layer are both aqueous systems, and the used solvent is a mixed solvent of water and alcohol, wherein the alcohol is a unit alcohol which can be mutually dissolved with water, and specifically comprises one or more of methanol, ethanol, isopropanol, n-propanol and n-butanol. The weight ratio of the water to the alcohol is preferably 50/1-1/10, and more preferably 20/1-1/5; when the adding amount of the alcohol is too small, the wettability of the coating liquid on the base film is poor, and the dispersion of the auxiliary agent in the coating liquid is influenced; an excessive amount of the alcohol is not economical, and thus the safety is lowered in the actual production process.
Base material
The base material is transparent plastic film material or film material of inorganic barrier layer deposited on the surface of transparent plastic film. The plastic film material comprises one of a polyethylene terephthalate film (PET), a polyethylene naphthalate film (PEN), an ethylene-tetrafluoroethylene copolymer (ETFE), polymethyl methacrylate (PMMA), a polypropylene film (PP), a polyamide film (PA), a polyethylene film (PE) and a polyimide film (PI). The inorganic barrier layer deposited on the surface of the transparent plastic film can be realized by a known physical or chemical method, specifically including vacuum thermal evaporation, electron beam Evaporation (EBPVD), magnetron sputtering, Plasma Enhanced Chemical Vapor Deposition (PECVD), atomic deposition and the like, and the inorganic barrier layer specifically includes a silicon oxide deposition layer, an aluminum oxide deposition layer, a silicon nitride deposition layer and the like.
Preparation of high light transmission barrier film
Both the high refractive index layer and the low refractive index layer of the present invention can be realized by a conventional coating method. For example: roll coating, gravure coating, blade coating, slot coating, extrusion coating, air knife coating, dip coating, spray coating.
The coated surface of the substrate needs to be subjected to surface treatment before coating, and the method for surface treatment is a known technology, such as: corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen, nitrogen or the like, glow discharge treatment, oxidation treatment using chemicals or the like, and the surface energy of the treated substrate is required to be not less than 40 dyn/cm. When the substrate is a thin film material deposited with an inorganic barrier layer, the coating surface is a deposited inorganic barrier layer surface.
The preparation method of the high light transmission barrier film comprises the following steps: firstly, coating a coating liquid of a high-refractive-index layer on a base material (1), and obtaining a high-refractive-index layer (2) after thermosetting is finished; then, the coating liquid of the low refractive index layer is directly coated on the high refractive index layer (2), and the low refractive index layer (3) is obtained by heat curing again.
The thickness of the high-refractive-index coating in the preparation process of the high-light-transmission barrier film is preferably 0.01-2 mu m; the thickness of the low-refractive index coating formed by the low-refractive index layer is preferably 0.2-10 μm, and more preferably 0.5-5 μm; the thickness ratio of the high refractive index layer to the low refractive index layer is preferably 1/20 to 10/1, and more preferably 1/10 to 5/1.
In the coating process, the temperature required by the thermosetting of the high refractive index layer (2) and the low refractive index layer (3) is preferably 45-250 ℃, more preferably 65-180 ℃, and the curing time is preferably 3 s-10 min, more preferably 10 s-5 min.
It should be further noted that the method for preparing the high light transmittance barrier film of the present invention is not limited to the above method, and a high refractive index layer and a low refractive index layer may be coated on both sides of the substrate, or alternatively coated on one side of the substrate to obtain a multi-layer structure barrier film.
The present invention will be further illustrated with reference to the following examples.
Example 1
Preparation of coating liquid for low refractive index layer:
487.8 parts by mass of polyacrylic acid aqueous solution (with the molecular weight of 5000) with the solid content of 20%, 24.4 parts by mass of gamma-aminopropyltriethoxysilane (KH550) and 487.8 parts by mass of polyethylene-vinyl alcohol (with the polymerization degree of 1700 and the alcoholysis degree of 80%) aqueous solution with the solid content of 10% are uniformly mixed and stirred at a high speed for 30min at 80 ℃ to obtain ZJ-1.
32 parts of tetraisopropoxysilane, 6.6 parts of titanium acetylacetonate, 5.4 parts of dilute hydrochloric acid (mass fraction: 0.1%), 356 parts of isopropanol and 600 parts of deionized water are uniformly mixed, and stirred at high speed at normal temperature to form a metal alkoxide hydrolysis condensate A-1 solution.
Uniformly mixing 180.5 parts by mass of ZJ-1 liquid and 810.5 parts by mass of metal alkoxide hydrolysis condensate A-1 solution, and stirring at high speed for 30min at normal temperature to obtain the low-refractive-index layer SC-1.
Preparation of coating liquid for high refractive index layer:
763.5 parts by mass of A-4 type acidic alumina sol (Dalian Snoor chemical) with the solid content of 10 percent, heating to 70 ℃, adding 142.0 parts by mass of titanium tetraisopropoxide while stirring, and finishing dropping in about 60 min; then heating to 95 ℃, continuing stirring at high speed for 30min, adding 94.5 parts by mass of nitric acid, and stirring at high speed for 1.5h at 95 ℃ to obtain AL-1.
38.0 parts by mass of 85% phosphoric acid, 332.4 parts by mass of deionized water, 88.7 parts by mass of methanol and 15.4 parts by mass of concentrated hydrochloric acid are uniformly mixed, then AL-1525.5 parts by mass are added, and the mixture is stirred at high speed for 30min at normal temperature to obtain a high-refractive-index layer DC-1.
Preparation of the barrier film:
carrying out corona or plasma treatment on the coating surface of the 12 mu mPE base film, coating liquid DC-1 by using micro-gravure coating equipment, and curing for 1min at the temperature of 120 ℃ to obtain a high-refractive-index layer with the dry thickness of 0.6 mu m; directly coating SC-1 on the surface of the high refractive index layer after coating, and curing for 2min at 120 ℃ to obtain a low refractive index layer with the dry thickness of 1.2 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
Example 2
Preparation of coating liquid for low refractive index layer:
487.8 parts by mass of polyacrylic acid aqueous solution (with the molecular weight of 5000) with the solid content of 20%, 24.4 parts by mass of gamma-aminopropyltriethoxysilane (KH550) and 487.8 parts by mass of polyvinyl alcohol (with the polymerization degree of 2600 and the alcoholysis degree of 80%) aqueous solution with the solid content of 5% are uniformly mixed and stirred at a high speed for 30min at 90 ℃ to obtain ZJ-2.
62 parts by mass of tetraisopropoxysilane, 8 parts by mass of zirconium acetylacetonate, 10 parts by mass of dilute hydrochloric acid (mass fraction: 0.1%), 380 parts by mass of isopropanol and 540 parts by mass of deionized water are uniformly mixed, and stirred at high speed at normal temperature to form a metal alkoxide hydrolysis condensate A-2 solution.
250 parts by mass of ester crosslinking modified polyacrylic acid liquid ZJ-2 and 700 parts by mass of metal alkoxide hydrolysis condensation compound A-2 solution are uniformly mixed, and stirred at high speed for 30min at normal temperature to obtain coating liquid SC-2 of the low refractive index coating.
Preparation of coating liquid for high refractive index layer:
the high refractive index layer DC-1 was prepared according to the formulation method of example 1.
Preparation of the barrier film:
corona or plasma treatment is carried out on the coating surface of the 50 mu m POT base film, DC-1 is coated by a micro-gravure coating device, and a high-refractive-index layer with the dry thickness of 0.8 mu m is obtained after curing for 40s at the temperature of 130 ℃; directly coating SC-2 on the surface coated with the high-refractive-index layer after coating, and curing for 1min at 130 ℃ to obtain a low-refractive-index layer with the dry thickness of 1.5 mu m; and taking down the film after coating, drying and storing to obtain the barrier film product.
Example 3
Preparation of coating liquid for low refractive index layer:
781.2 parts by mass of polyacrylic acid aqueous solution (with the molecular weight of 250000) with the solid content of 15%, 11.4 parts by mass of gamma-mercaptopropyltriethoxysilane (KH580) and 207.4 parts by mass of 10% polyvinyl alcohol (with the polymerization degree of 1700 and the alcoholysis degree of 99%) aqueous solution are uniformly mixed and stirred at a high speed for 30min at 95 ℃ to obtain the ester crosslinking modified polyacrylic acid solution ZJ-3.
Tetraethoxysilane 65 parts by mass, dilute hydrochloric acid 15 parts by mass (mass fraction 0.1%), methanol 380 parts by mass and deionized water 540 parts by mass are uniformly mixed, and stirred at high speed at normal temperature to form a metal alkoxide hydrolysis condensation compound A-3 solution.
750 parts by mass of ester crosslinking modified polyacrylic acid liquid ZJ-3 and 250 parts by mass of metal alkoxide hydrolysis condensation compound A-3 solution are uniformly mixed, and stirred at high speed for 30min at normal temperature to obtain coating liquid SC-3 of the low refractive index coating.
Preparation of coating liquid for high refractive index layer:
a coating solution DC-1 for a high refractive index coating was prepared in accordance with the preparation method of example 1.
Preparation of the barrier film:
corona or plasma treating the coated surface of 125 μm PE base film, coating DC-1 with micro-gravure coating equipment, curing at 135 deg.C for 1min to obtain high refractive index film with dry thickness of 0.8 μmA refractive index coating; directly coating SC-3 on the surface coated with the high-refractive-index layer after coating, and curing for 2min at 120 ℃ to obtain a low-refractive-index layer with the dry thickness of 1.5 mu m; taking down after coating, drying and storing to obtain the barrier film product (the light transmittance is 91 percent, WVTR0.15g/m)2.d，OTR0.15cc/m2.d)。
Example 4
Preparation of coating liquid for low refractive index layer:
790.3 parts by mass of polyacrylic acid aqueous solution (with the molecular weight of 500000) with the solid content of 10%, 12.1 parts by mass of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH792) and 197.6 parts by mass of polyvinyl alcohol (with the polymerization degree of 1700 and the alcoholysis degree of 99%) aqueous solution with the solid content of 10% are uniformly mixed and stirred at a high speed for 30min at 75 ℃ to obtain the ester crosslinking modified polyacrylic acid solution ZJ-4.
Tetraethoxysilane 35.4 parts by mass, silane coupling agent (A187)7.3 parts by mass, dilute hydrochloric acid 6.6 parts by mass (mass fraction 0.1%), methanol 287.4 parts by mass, and deionized water 663.3 parts by mass were mixed uniformly, and stirred at high speed at normal temperature to form a metal alkoxide hydrolysis condensate A-4 solution.
750 parts by mass of ester crosslinking modified polyacrylic acid liquid ZJ-4 and 250 parts by mass of metal alkoxide hydrolysis condensation compound A-4 are uniformly mixed, and stirred at high speed for 30min at normal temperature to obtain coating liquid SC-4 of the low refractive index layer.
Preparation of coating liquid for high refractive index layer:
a coating solution DC-1 for a high refractive index coating was prepared in accordance with the preparation method of example 1.
Preparation of the barrier film:
carrying out corona or plasma treatment on the coating surface of the 12 mu mPE base film, coating DC-1 by using micro-gravure coating equipment, and curing for 40s at 120 ℃ to obtain a high-refractive-index layer with the dry thickness of 0.4 mu m; directly coating SC-4 on the surface of the high refractive index layer after coating, and curing for 2min at 120 ℃ to obtain a low refractive index layer with the dry thickness of 1.0 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
Example 5
Preparation of coating liquid for low refractive index layer:
coating solution SC-4 for a low refractive index layer was prepared in the same manner as in example 4.
Preparation of high refractive index layer:
773.5 parts by mass of A-4 type acidic alumina sol (Dalian Snoo chemical) with the solid content of 5 percent, heating to 70 ℃, adding 128.0 parts by mass of neutral silica sol (Zhejiang Deliki) with the solid content of 25 percent and 4.4 parts by mass of zirconium acetylacetonate while stirring, and finishing dropping in about 30 min; then heating to 95 ℃, continuing stirring at high speed for 30min, adding 94.1 parts by mass of acetic acid, and stirring at high speed for 1.5h at 95 ℃ to obtain the nano oxide AL-2 dispersion liquid.
17.5 parts by mass of 85% phosphoric acid, 400.4 parts by mass of deionized water, 106.0 parts by mass of methanol and 20 parts by mass of trifluoroacetic acid are uniformly mixed, then 456.1 parts by mass of nano oxide AL-2 dispersion liquid is added, and the mixture is stirred at high speed for 30min at normal temperature to obtain coating liquid DC-2 of the high-refractive-index layer.
Preparation of the barrier film:
carrying out corona or plasma treatment on the coating surface of the 50 mu m ETFE basal membrane, coating DC-2 by using micro-gravure coating equipment, and curing for 30s at 130 ℃ to obtain a high-refractive-index coating with the dry thickness of 0.3 mu m; directly coating SC-4 on the surface coated with the high-refractive-index layer after coating, and curing at 130 ℃ for 40s to obtain a low-refractive-index layer with the dry thickness of 1.0 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
Example 6
Preparation of coating liquid for low refractive index layer:
coating solution SC-4 for the low refractive index layer was prepared as in example 4.
Preparation of high refractive index layer:
811.7 parts by mass of distilled water is heated to 70 ℃, 174.2 parts by mass of aluminum triisopropoxide is added while stirring, and the addition is finished within about 30 min; then heating to 95 ℃, continuing stirring at high speed for 30min, adding 14.1 parts by mass of 60% nitric acid, and stirring at high speed for 1.5h at 95 ℃ to obtain the nano oxide AL-3 dispersion.
4.5 parts by mass of 85% phosphoric acid, 445.0 parts by mass of deionized water, 119.0 parts by mass of methanol, 16.5 parts by mass of concentrated hydrochloric acid and 0.70 part by mass of 5% aminotrimethylene phosphonic acid are uniformly mixed, then 414.3 parts by mass of nano oxide AL-3 dispersion liquid is added, and the mixture is stirred at high speed for 30min at normal temperature to obtain coating liquid DC-3 of the high-refractive-index layer.
Preparing an anti-reflection-barrier coating:
carrying out corona or plasma treatment on the coating surface of the 25 mu m ETFE basal membrane, coating DC-3 by using micro-gravure coating equipment, and curing for 30s at the temperature of 130 ℃ to obtain a high-refractive-index layer with the dry thickness of 0.3 mu m; directly coating SC-4 on the surface coated with the high-refractive-index layer after coating, and curing for 30s at 130 ℃ to obtain a low-refractive-index layer with the dry thickness of 1.0 mu m; and taking down the coating after coating, drying and storing to obtain the resistance-increasing diaphragm product.
Example 7
Coating solution SC-4 for the low refractive index layer was prepared as in example 4.
Coating solution DC-3 for the high refractive index layer was prepared as in example 6.
Preparation of the barrier film:
carrying out corona or plasma treatment on the coating surface of the 18-micron BOPP film, coating DC-3 by using micro-gravure coating equipment, and curing for 1min at the temperature of 100 ℃ to obtain a high-refractive-index layer with the dry thickness of 0.5 micron; directly coating SC-4 on the surface coated with the high-refractive-index layer after coating, and curing for 2.5min at 100 ℃ to obtain a low-refractive-index layer with the dry thickness of 1.2 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
Example 8
Coating solution SC-3 for the low refractive index layer was prepared as in example 3.
Coating solution DC-1 for the high refractive index layer was prepared as in example 1.
Preparation of the barrier film:
corona or plasma treatment is carried out on the coating surface of the base film of 50 mu mPI, DC-1 is coated by a micro-gravure coating device, and the high-refractive-index layer with the dry thickness of 0.5 mu m is obtained after curing for 10s at the temperature of 180 ℃; directly coating SC-3 on the surface coated with the high-refractive-index layer after coating, and curing at 155 ℃ for 20s to obtain a low-refractive-index layer with the dry thickness of 1.5 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
Example 9
Preparation of coating liquid for low refractive index layer:
487.8 parts by mass of polyacrylic acid aqueous solution (with the molecular weight of 250000) with the solid content of 15%, 14.4 parts by mass of gamma-aminopropyltriethoxysilane (KH550), 11.0 parts by mass of gamma-mercaptopropyltriethoxysilane (KH580) and 487.8 parts by mass of polyethylene-vinyl alcohol (with the polymerization degree of 2400 and the alcoholysis degree of 85%) aqueous solution with the solid content of 5% are uniformly mixed, and then the mixture is stirred at a high speed for 30min at the temperature of 80 ℃ to obtain ZJ-5.
Tetraethoxysilane 64 parts by mass, titanium tetraisopropoxide 13.2 parts by mass, dilute hydrochloric acid 5.4 parts by mass (mass fraction 0.1%), methanol 356 parts by mass and deionized water 561.4 parts by mass are uniformly mixed, and stirred at high speed at normal temperature to form a metal alkoxide hydrolysis condensate A-5 solution.
380.5 parts by mass of ester crosslinking modified polyacrylic acid liquid ZJ-5 and 610.5 parts by mass of metal alkoxide hydrolysis condensation compound A-1 solution are uniformly mixed, and the mixture is stirred at a high speed for 30min at normal temperature to obtain a coating liquid SC-5 of the low refractive index layer.
Preparation of high refractive index layer:
a coating solution DC-1 for a high refractive index coating was prepared in accordance with the preparation method of example 1.
Preparing an anti-reflection-barrier coating:
corona or plasma treatment is carried out on the coating surface of the 250 mu mPE base film, DC-1 is coated by a micro-gravure coating device, and a high-refractive-index layer with the dry thickness of 0.8 mu m is obtained after curing for 30s at 135 ℃; directly coating SC-5 on the surface coated with the high-refractive-index coating after coating, and curing for 2min at 120 ℃ to obtain a low-refractive-index layer with the dry thickness of 2.0 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
Example 10
Coating solution SC-3 for the low refractive index layer was prepared as in example 3.
Preparation of coating liquid for high refractive index layer:
710.0 parts by mass of deionized water, heating to 70 ℃, adding 41.0 parts by mass of aluminum triisopropoxide, 140.7 parts by mass of titanium tetraisopropoxide, 5.3 parts by mass of zinc acetate and 8.5 parts by mass of zirconium acetylacetonate while stirring, and dripping the mixture for about 60 min; then heating to 95 ℃, continuing stirring at high speed for 30min, adding 94.5 parts by mass of nitric acid, and stirring at high speed for 1.5h at 95 ℃ to obtain AL-4.
38.0 parts by mass of 85% phosphoric acid, 236.0 parts by mass of deionized water, 115 parts by mass of methanol and 15.5 parts by mass of trifluoroacetic acid were uniformly mixed, and then AL-4595.5 parts by mass was added thereto, and the mixture was stirred at high speed at normal temperature for 30 minutes to obtain a coating liquid DC-4 of a high refractive index layer.
Preparation of the barrier film:
performing corona or plasma treatment on the silicon oxide-plated surface of the silicon oxide film, coating DC-4 with a micro-gravure coating device, and curing at 120 ℃ for 1min to obtain a high-refractive-index layer with a dry thickness of 0.3 mu m; directly coating SC-3 on the surface coated with the high-refractive-index layer after coating, and curing for 2min at 120 ℃ to obtain a low-refractive-index layer with the dry thickness of 1.2 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
Example 11
Coating solution SC-3 for the low refractive index layer was prepared as in example 3.
Coating solution DC-1 for the high refractive index layer was prepared as in example 1.
Preparation of the barrier film:
corona or plasma treatment is carried out on the aluminum oxide plating surface of the aluminum oxide plating film, DC-1 is coated by micro-gravure coating equipment, and the high refractive index layer is obtained by curing for 1min at the temperature of 120 ℃ and the dry thickness of 0.5 mu m; directly coating SC-3 on the surface coated with the high-refractive-index layer after coating, and curing for 1.5min at 120 ℃ to obtain a low-refractive-index layer with the dry thickness of 1.5 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
Example 12
Coating solution SC-4 for the low refractive index layer was prepared as in example 4.
Coating solution DC-3 for the high refractive index layer was prepared as in example 6.
Preparation of the barrier film:
performing corona or plasma treatment on the silicon oxide-plated surface of the silicon oxide film, coating DC-3 by using micro-gravure coating equipment, and curing at 120 ℃ for 1min to obtain a high-refractive-index layer with the dry thickness of 0.3 mu m; directly coating SC-4 on the surface coated with the high-refractive-index layer after coating, and curing for 2min at 120 ℃ to obtain a low-refractive-index layer with the dry thickness of 1.0 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
Example 13
Coating solution SC-4 for the low refractive index layer was prepared as in example 4.
Coating solution DC-4 for the high refractive index layer was prepared as in example 9.
Preparation of the barrier film:
performing corona or plasma treatment on the silicon oxide-plated surface of the silicon nitride film, coating DC-4 with micro-gravure coating equipment, and curing at 120 ℃ for 1min to obtain a high-refractive-index layer with the dry thickness of 0.3 mu m; directly coating SC-4 on the surface coated with the high-refractive-index layer after coating, and curing for 1min at 120 ℃ to obtain a low-refractive-index layer with the dry thickness of 1.0 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
Comparative example 1
Coating solution SC-3 for the low refractive index layer was prepared as in example 3.
Preparation of the barrier film:
carrying out corona or plasma treatment on the coating surface of the 12 mu mPE base film, coating SC-3 by using micro-gravure coating equipment, and curing for 2min at 120 ℃ to obtain a low-refractive-index layer with the dry thickness of 1.5 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
Comparative example 2
Coating solution DC-1 for the high refractive index layer was prepared as in example 1.
Preparation of the barrier film:
carrying out corona or plasma treatment on the coating surface of the 12 mu mPE base film, coating DC-1 by using micro-gravure coating equipment, and curing for 2min at 120 ℃ to obtain a low-refractive-index layer with the dry thickness of 1.0 mu m; and taking down the coated film after coating, drying and storing to obtain the barrier film product.
The total light transmittance and the barrier property of the prepared anti-reflection and barrier coating are respectively tested in the above examples and comparative examples, and the specific test conditions are shown in tables 1 and 2.
TABLE 1
Figure BDA0002613235040000151
As can be seen from table 1, in each example, the high refractive index layer and the low refractive index layer are used to prepare the anti-reflection and barrier coating, so that the water resistance and oxygen resistance of different substrates are improved, and the light transmittance of the substrates is further improved; comparative examples 1, 2 illustrate that the use of either the high refractive index layer or the low refractive index layer alone is significantly lower in barrier and light transmission properties than the results tested in the examples.
TABLE 2
Figure BDA0002613235040000161
As can be seen from table 2, the high refractive index layer and the low refractive index layer of the present invention can be used on the substrate coated with the inorganic oxide barrier layer to further reduce the barrier property thereof, and simultaneously improve the light transmittance of the substrate coated with the inorganic oxide barrier layer, thereby being more beneficial to the application in the electronic packaging field such as solar cell packaging, OLED packaging, etc.
The above description is only a preferred embodiment, but the present invention is not limited to other embodiments. Various equivalent changes, substitutions and improvements may occur to those skilled in the art and are intended to be included within the scope of the present invention.
Methods for testing the performance of the examples and comparative examples above:
1. measurement of coating thickness
The thickness of the hardened layer of the surface hardening film of the optical functional film is tested according to the national standard GB/T33051-2016.
2. Measurement of light transmittance
According to the national standard GB/T2410-.
3. Refractive index measurement
An Abbe refractometer is adopted to measure the refractive index of liquid chemical products (20 ℃) according to the national standard GB/T6488-
4. Determination of oxygen permeability of film
The oxygen permeability tester marked by Guangzhou is adopted to test according to national standard GB/T19789-.
5. Determination of Water Permeability of film
The test is carried out by adopting an American MOCON moisture permeability instrument according to the national standard GB/T21529-.

Claims (13)

1. The high light transmission barrier film is characterized in that the structure of the high light transmission barrier film sequentially comprises a base material, a high refractive index layer and a low refractive index layer; the high-refractive-index layer comprises the following components in parts by weight:
1 to 50 parts of particles having a high refractive index,
3 to 100 parts of nano-oxide,
0.5 to 50% of a phosphorus-containing compound,
0.5-70% of an acid catalyst;
the low refractive index layer comprises the following components in parts by weight:
4 to 200 of a carboxyl group-containing polymer,
1 to 100 parts of a water-soluble polymer containing hydroxyl groups,
0.01 to 20 parts of a coupling agent having a group reactive with a carboxyl group,
0.3 to 80 parts by mass of a hydrolytic condensation product of a silicon alkoxide,
0.015-20 parts of resin cross-linking agent.
2. The barrier film according to claim 1, wherein the high refractive index layer has a refractive index of 1.5 to 2.0 and a thickness of 0.01 to 2 μm; the low refractive index layer has a refractive index of 1.3-1.5 and a thickness of 0.2-10 μm; the thickness ratio of the high refractive index layer to the low refractive index layer is 1/20-10/1.
3. The high light transmission barrier film of claim 1 wherein the high light transmission barrier filmThe high refractive index particles in the refractive index layer are composed of a compound (L) bonded with a characteristic group capable of hydrolysis, and the compound (L) has a general formula of MXmWherein M is one element of Ti, Zr, Zn, Mg or Ca, X is one element of methoxy, ethoxy, isopropoxy, n-butoxy, acetylacetone, carboxyl, nitro, F, Cl, Br or I, and M is a positive integer of 1-4.
4. The barrier film with high light transmittance according to claim 3, wherein the nano oxide in the high refractive index layer is one or two of nano aluminum oxide and nano silicon oxide, and the particle size is 10nm to 200 nm.
5. The barrier film according to claim 4, wherein the amount of M element in the high refractive index particles in the high refractive index layer (n) is equal to or greater than the amount of M element in the high refractive index particles in the high refractive index layer3) With the amount of metal element in the nano-oxide (n)2) N is not less than 0.013/n2≤3.5。
6. The barrier film of claim 5 wherein the phosphorous-containing compound in the high refractive index layer comprises one or more of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, nitrilotris (methylenephosphonic acid), or N, N, N, N-ethylenediaminetetra (methylenephosphonic acid).
7. The barrier film of claim 6 wherein the amount of phosphorus in the phosphorus-containing compound is (n) the amount of phosphorus in the film1) And the amount of metal element substances (n) in the nano oxide2) And the amount of M element (n) in the high-refractive-index particles3) N is more than or equal to 0.11/(n2+n3)≤2.5。
8. The high light transmission barrier film of claim 7 wherein the acid catalyst comprises one or more of nitric acid, hydrochloric acid, sulfuric acid, boric acid, formic acid, acetic acid, butyric acid, trifluoroacetic acid, citric acid, tartaric acid, lactic acid, oxalic acid, or maleic acid.
9. The barrier film according to claim 8, wherein the polymer containing carboxyl groups is one of polyacrylic acid, polymethacrylic acid and poly (acrylic acid/methacrylic acid) copolymer, and the molecular weight is controlled in the range of 3000 to 1500,000.
10. The barrier film according to claim 9, wherein the water-soluble polymer containing hydroxyl groups is one of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, polysaccharides, chitosan and cellulose, the degree of polymerization is controlled to 500 to 3000, and the degree of alcoholysis is controlled to 80 to 99.99%.
11. The barrier film according to claim 10, wherein the coupling agent having a group reactive with a carboxyl group is a coupling agent having an amino group, a mercapto group, and an epoxy group, and is selected from one or more of γ -aminopropyltrimethoxysilane (KH540), γ -aminopropyltriethoxysilane (KH550), diethylaminomethyltriethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane (KH792), γ -mercaptopropyltrimethoxysilane (KH590), γ -mercaptopropyltriethoxysilane (KH580), γ - (2, 3-glycidoxy) propyltrimethoxysilane, and γ - (2, 3-glycidoxy) propyltriethoxysilane.
12. The barrier film of claim 11, wherein the silicon alkoxide salt hydrolytic condensate is one or more of tetramethoxysilane, tetraethoxysilane, trimethoxy aluminum, n-propyltrimethoxysilane, methyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, or 1,3, 5-tris (3-trimethoxysilylpropyl) isocyanurate.
13. The barrier film of claim 12 wherein the resin crosslinking agent is one or more of zinc acetate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium polyacetylacetonate, titanium polyhydroxystearate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, or zirconium acetate.
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