CN113621280A - Aqueous coating liquid and gas barrier film - Google Patents

Aqueous coating liquid and gas barrier film Download PDF

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Publication number
CN113621280A
CN113621280A CN202110811678.8A CN202110811678A CN113621280A CN 113621280 A CN113621280 A CN 113621280A CN 202110811678 A CN202110811678 A CN 202110811678A CN 113621280 A CN113621280 A CN 113621280A
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layer
aqueous coating
gas barrier
film
silane
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王群
刘墨宁
宣玉凤
刘军虎
刘稀蒙
冯铭竹
赵伟涛
纪雪梅
宋鑫
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China Lucky Group Corp
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China Lucky Group Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08J7/048—Forming gas barrier coatings
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    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
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    • C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
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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
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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    • 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
    • C09D7/61—Additives non-macromolecular inorganic
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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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
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    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2429/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Abstract

The invention discloses an aqueous coating liquid and a gas barrier film. The aqueous coating liquid includes: 100 parts by weight of a water-soluble polymer and 50 to 1500 parts by weight of a siloxane hydrolyzateAccording to SiO2Calculated) nano oxide, 0.01-10 parts by weight of assistant and 1000-12000 parts by weight of solvent; wherein the siloxane hydrolysate is SiO by weight2Calculated) and the weight ratio of the nano oxide is 1 (2.0-50). The gas barrier film prepared from the aqueous coating liquid has excellent gas barrier capability, and the aqueous coating liquid has good stability and strong coating property, and is suitable for mass coating production.

Description

Aqueous coating liquid and gas barrier film
Technical Field
The present invention relates to the field of materials, and more particularly, to an aqueous coating liquid and a gas barrier film.
Background
Foods, medicines, electronic products, and the like are easily deteriorated by the action of gases such as water vapor and oxygen, and in order to maintain their performance and function, they need to be packaged with a material having a sufficient gas barrier ability. Gas barrier materials that are currently more commonly used include: polyvinylidene chloride films, multilayer co-extruded EVOH, metal foils or plastic films with a deposited metal layer, vapor-deposited oxide type films, and the like.
Polyvinylidene chloride films are excellent in barrier properties and are not sensitive to moisture, but are sensitive to temperature and generate dioxin, which is very toxic, after incineration, and thus are gradually being replaced by other barrier materials. The deterioration of the gas barrier properties of multilayer coextruded EVOH is very severe with increasing humidity, and thus the application fields thereof are also greatly limited. Although metal foil or plastic film having a metal layer deposited thereon has excellent barrier properties and gas barrier properties at high temperatures and humidity, there are problems that the contents are invisible, microwave heating is not possible, and waste after use is difficult to handle. The vapor deposited oxide film has the advantages of transparency, no pollution, insignificant variation of gas barrier performance with temperature and humidity, capability of microwave heating and the like, but the barrier performance of the vapor deposited oxide film is seriously degraded after boiling or pressure cooking treatment. As can be seen, the existing gas barrier material films still remain to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Accordingly, an object of the present invention is to provide an aqueous coating liquid and a gas barrier film. The gas barrier film prepared from the aqueous coating liquid has excellent gas barrier capability, and the aqueous coating liquid has good stability and strong coating property, and is suitable for mass coating production.
In one aspect of the present invention, an aqueous coating solution is provided. According to an embodiment of the present invention, the aqueous coating liquid includes: 100 parts by weight of a water-soluble polymer and 50 to 1500 parts by weight of a siloxane hydrolyzate (the weight is SiO)2Calculated) nano oxide, 0.01-10 parts by weight of assistant and 1000-12000 parts by weight of solvent; wherein the siloxane hydrolysate is SiO by weight2Calculated) and the weight ratio of the nano oxide is 1 (2.0-50).
In the aqueous coating solution according to the above embodiment of the present invention, a network structure may be formed between the water-soluble polymer and the siloxane hydrolysate, and the two network structures may be bonded to each other by a chemical bond, thereby improving the stability of a coating layer formed from the aqueous coating solution under high temperature and high humidity conditions. In addition, by controlling the content of the siloxane hydrolysate and the nano oxide within the range, the nano oxide can be filled in the gaps of the network structure, so that the volume shrinkage of the coating in the film forming process and the subsequent high-temperature cooking process can be reduced, and the influence of stress on other layer structures in the gas barrier film product prepared from the aqueous coating liquid is inhibited. Therefore, the prepared gas barrier film has excellent gas barrier capability, can be used in the fields of food packaging, medical packaging, electronic product packaging and the like, and the aqueous coating liquid has good stability and strong coating property and is suitable for mass coating production.
In addition, the aqueous coating liquid according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the water soluble polymer is at least one of silane modified polyvinyl alcohol, silane modified starch, silane modified cellulose, silane modified chitosan.
In some embodiments of the invention, the water soluble polymer is a silane modified polyvinyl alcohol.
In some embodiments of the present invention, the silane-modified polyvinyl alcohol has a mole ratio of silane groups to hydroxyl groups of 0.5/99.5 to 5/95, a molecular weight of 1000 to 5000, and a degree of alcoholysis of 80 to 99.9%.
In some embodiments of the invention, the siloxane hydrolyzate is Si (OR)4Hydrolyzing under the condition that the pH value is less than or equal to 4 to obtain a product, wherein R is C1-8An alkyl group.
In some embodiments of the present invention, the nano oxide is at least one selected from the group consisting of alumina, silica, zinc oxide, titanium oxide, zirconia, magnesium carbonate, calcium carbonate, and barium sulfate, and has an average particle size of 1 to 100 nm.
In some embodiments of the present invention, the auxiliary agent is selected from at least one of a wetting agent, a coupling agent, an adhesion promoter, and a leveling agent.
In some embodiments of the present invention, the solvent is a mixed solvent of water and alcohol.
In another aspect of the invention, the invention features a gas barrier film. According to an embodiment of the present invention, the gas barrier film includes: a base film layer and a barrier layer formed on one or both side surfaces of the base film layer, the barrier layer being formed from the aqueous coating liquid of the above embodiment.
The gas barrier film according to the above embodiment of the present invention can obtain excellent gas barrier ability by forming the barrier layer using the aqueous coating solution as described above, can be used in the fields of food packaging, medical packaging, electronic product packaging, and the like, and is suitable for mass production.
In addition, the gas barrier film according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the thickness of the barrier layer is 0.05 to 5 μm.
In some embodiments of the present invention, the base film layer is a polyolefin-based film, a polyester-based film, or a polyamide-based film.
In some embodiments of the present invention, an inorganic material layer is further included between the base film layer and the barrier layer.
In some embodiments of the invention, the inorganic material layer is formed of at least one of alumina, silica, iron oxide, zirconia, and silicon nitride.
In some embodiments of the present invention, the thickness of the inorganic material layer is 5 to 500 nm.
In some embodiments of the present invention, each of the barrier layers and the inorganic material layer includes a plurality of layers and is alternately arranged in a thickness direction of the base film layer.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic view of the structure of a gas barrier film according to one embodiment of the present invention;
fig. 2 is a schematic view of the structure of a gas barrier film according to another embodiment of the present invention;
fig. 3 is a schematic view of the structure of a gas barrier film according to still another embodiment of the present invention;
fig. 4 is a schematic view of the structure of a gas barrier film according to still another embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In one aspect of the present invention, an aqueous coating solution is provided. According to an embodiment of the present invention, the aqueous coating liquid includes: 100 parts by weight of a water-soluble polymer,50-1500 parts by weight of siloxane hydrolysate (SiO by weight)2Calculated) nano oxide, 0.01-10 parts by weight of assistant and 1000-12000 parts by weight of solvent; wherein the siloxane hydrolysate is SiO by weight2Calculated) and the weight ratio of the nano oxide is 1 (2.0-50).
Specifically, in the aqueous coating liquid of the present invention, a siloxane hydrolyzate (in terms of SiO by weight)2Calculated by weight) and nano-oxide can be 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500 and the like, the auxiliary agent can be 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and the like, the solvent can be 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000 and the like, and the siloxane hydrolysate (calculated by weight of SiO) can be obtained2Calculated) and the nano-oxide can be 1:2.0, 1:3.0, 1:4.0, 1:5.0, 1:6.0, 1:7.0, 1:8.0, 1:9.0, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50 and the like. The inventors found that if the weight ratio of the siloxane hydrolyzate to the nano oxide is too low, the strength of the action between the organic component and the inorganic component is insufficient, and the high-temperature retort resistance of the coating layer formed from the aqueous coating liquid is not good; if the weight ratio of the siloxane hydrolysate to the nano oxide is too high, the problem of large volume shrinkage in the curing of the coating exists, and the flatness and the barrier property of the film are influenced.
According to some embodiments of the present invention, the water-soluble polymer may be at least one of silane-modified polyvinyl alcohol, silane-modified starch, silane-modified cellulose, and silane-modified chitosan. More preferably, the water-soluble polymer is a silane-modified polyvinyl alcohol. In addition, as long as the intention of the present invention is satisfied, the specific method of silane modification is not particularly limited, and for example, the modification may be performed by copolymerizing a vinyl acetate monomer with a silane olefin monomer and then saponifying the resultant; or reacting a silane coupling agent with one end containing isocyanate group and/or aldehyde group with hydroxyl in the substance to be modified.
According to some embodiments of the present invention, the silane-modified polyvinyl alcohol may have a mole ratio of silane groups to hydroxyl groups of 0.5/99.5 to 5/95, a molecular weight of 1000 to 5000, and a alcoholysis degree of 80 to 99.9%. Specifically, the molar ratio of the silane groups to the hydroxyl groups in the silane-modified polyvinyl alcohol may be 0.5/99.5, 1/99, 1.5/98.5, 2/98, 2.5/97.5, 3/97, 3.5/96.5, 4/96, 4.5/95.5, 5/95, etc., and the degree of alcoholysis of the silane-modified polyvinyl alcohol may be 80%, 82%, 85%, 88%, 90%, 92%, 95%, 99%, 99.9%, etc. The inventors have found that when the molar ratio of the silane group to the hydroxyl group in the silane-modified polyvinyl alcohol is less than 0.5/99.5, the strength of action between the organic component and the inorganic component is insufficient, and the high-temperature retort resistance of a coating layer formed from an aqueous coating liquid is poor; when the molar ratio of the silane group to the hydroxyl group in the silane-modified polyvinyl alcohol is higher than 5/95, the oxygen barrier ability of the coating layer formed from the aqueous coating solution may be adversely affected. In some embodiments of the present invention, the silane-modified polyvinyl alcohol may be commercially available products, such as Coly R-3109, Coly R-2105, Wacker P-6060, and the like.
According to some embodiments of the invention, the siloxane hydrolysate is an alkoxysilane (siloxane) Si (OR)4Hydrolyzing under the condition that the pH value is less than or equal to 4 to obtain a product, wherein R is C1-8An alkyl group. More preferably, R is C1-4Alkyl groups such as methyl, ethyl, n-propyl, n-butyl, and the like. As alkoxysilanes (siloxanes) Si (OR)4Specific examples of (3) include tetramethoxysilane Si (OCH)3)4Tetraethoxysilane Si (OC)2H5)4Tetrapropoxysilane Si (OC)3H7)4Tetra-butoxysilane Si (OC)4H9)4And the like. The alkoxysilane may undergo a series of hydrolytic condensation reactions under the catalysis of acid or base, and in order to improve the degree of miscibility with the water-soluble polymer, hydrolysis is preferably carried out at a pH of 4 or less, whereby the stability of the hydrolysate can be further improved. If the system pH is>4, stability of the hydrolysate is reduced. The kind of acid used for adjusting the pH of the system is not particularly limited, and may be, for exampleInorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid are used.
According to some embodiments of the present invention, the nano-oxide may be at least one selected from alumina, silica, zinc oxide, titanium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, and barium sulfate, and the average particle size of the nano-oxide may be 1 to 100nm, for example, 1nm, 3nm, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, and the like, and more preferably 3 to 50 nm. If the particle size of the nano oxide is too small, the preparation and storage are difficult, and if the particle size of the nano oxide is too large, the barrier property of the coating formed from the aqueous coating liquid is affected. In addition, according to some embodiments of the present invention, the nano-oxide may be surface-modified before use, for example, the surface of the nano-oxide may be modified by using a silane coupling agent, a titanate coupling agent, or a phosphoric acid coupling agent, so that the hydroxyl content on the surface of the nano-oxide is 1 to 100mmol/nm2So that better dispersing performance is obtained. The inventors have found that if the hydroxyl group content of the surface of the nano-oxide is too low, the oxygen barrier ability of the coating layer formed from the aqueous coating liquid may be adversely affected; if the hydroxyl group content on the surface of the nano-oxide is too high, the performance of the coating formed by the aqueous coating liquid to resist high temperature and high humidity is affected.
According to some embodiments of the present invention, the solvent is a mixed solvent of water and alcohol. The alcohol is a water-miscible monohydric alcohol, and may be at least one selected from methanol, ethanol, isopropanol, and n-propanol, for example. The volume ratio of the water to the alcohol is preferably 50/1-1/10, and more preferably 20/1-1/5. The inventors found that if the content of the alcohol in the mixed solvent is too low, it may cause deterioration in wettability of the aqueous coating liquid and affect effective dispersion of the auxiliary; if the content of the alcohol in the mixed solvent is too high, safety in the production process is affected and it is uneconomical.
In addition, the aqueous coating liquid of the present invention further contains an auxiliary agent, and thus can obtain more excellent performance in terms of coating effect, coating appearance, and the like. The specific kind of the auxiliary agent is not particularly limited, and according to some embodiments of the present invention, the auxiliary agent may be selected from at least one of a wetting agent, a coupling agent, an adhesion promoter, and a leveling agent.
For ease of understanding, the following description will be made of the method for preparing the aqueous coating liquid.
As mentioned above, the alkoxysilane undergoes a series of hydrolytic condensation reactions under the catalysis of acid to form a homogeneous system. The inventors found that suppressing the formation of large particles during hydrolysis is advantageous for improving the retort resistance of a coating layer formed from an aqueous coating solution, and that the continued occurrence of condensation reaction will have a decisive effect on the enlargement of particles, that is, in order to obtain an alkoxysilane hydrolysate of large particles, the reaction rate of condensation reaction needs to be suppressed. Further, the inventors have found, through intensive studies, that the condensation reaction rate can be effectively suppressed by maintaining the pH of the reaction system at 4 or less, thereby obtaining large-particle alkoxysilane hydrolysate. The condensation reaction rate can be controlled by the concentration of the alkoxysilane compound in the reaction system, and the mass ratio of the alkoxysilane compound to the solution during hydrolysis is controlled to 50% or less, preferably 40% or less, and more preferably 30% or less, and the mass ratio of the alkoxysilane compound to the solution during hydrolysis is more than 5% from the viewpoint of ease of handling. In addition, in the case where a water-soluble polymer is present in the reaction system, the condensation reaction can be further suppressed. On the other hand, the inventors have found that it is advantageous to control the system temperature during the hydrolysis, and the hydrolysis of the alkoxysilane compound is an exothermic process, and the reaction system temperature can be controlled to 2 to 50 ℃, more preferably 5 to 40 ℃. This provides a more effective inhibition of the hydrolysis reaction rate.
For the water-soluble polymer, it may be dissolved in advance with a solvent and added to the reaction system before, during or after the hydrolysis of the alkoxysilane compound.
The nano oxide may be added to the reaction system in a powder state or a dispersion state before, during, or after the hydrolysis of the alkoxysilane compound.
The assistant is preferably added to the reaction system after the alkoxysilane compound is added and the water-soluble polymer and the nano oxide are added after hydrolysis, and the performance of the aqueous coating solution is further adjusted.
In another aspect of the invention, the invention features a gas barrier film. Referring to fig. 1 and 2, according to an embodiment of the present invention, the gas barrier film includes a base film layer 1 and a barrier layer 2. Wherein the barrier layer 2 is formed on one or both surfaces of the base film layer 1, and the barrier layer 2 is formed from the aqueous coating solution of the above embodiment.
According to some embodiments of the present invention, the thickness of the barrier layer may be 0.05 to 5 μm, such as 0.05 μm, 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, and the like. When the thickness of the barrier layer is within the above range, the barrier properties and stress accumulation of the barrier layer can be improved. If the thickness of the barrier layer is too small, it is difficult to exert the barrier ability; if the thickness of the barrier layer is too great, the coating may crack, affecting barrier properties and interlayer adhesion.
Specific types of the base film layer in the gas barrier film of the present invention are not particularly limited, and may be selected from, for example, (1) transparent resin films, amorphous polyolefin films including polyolefins, cyclic polyolefins, and the like, which are polymers or copolymers of monomers such as ethylene, propylene, butene, and the like; (2) polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate; (3) polyamide-based films such as nylon 6, nylon 66, and nylon 12; (4) EVOH, polyvinyl butyral, fluorine resins, biodegradable resins, and the like, which are partial hydrolyzates of ethylene-vinyl acetate copolymers. The thickness of the base film layer may be 5 to 300 μm, preferably 5 to 150 μm.
According to some embodiments of the present invention, a primer layer (not shown in the drawings) is further formed on the surface of the base film layer, the primer layer can be obtained by performing activation treatment such as corona and/or plasma treatment on the base film layer, the material of the primer layer can be one or more of solvent-based or water-soluble polyester resin, polyurethane resin, acrylic resin, styrene resin and amino resin, and the thickness of the primer layer can be 0.005 to 5 μm, and preferably 0.01 to 1 μm. If the thickness of the bottom layer is too small, the defects on the surface of the base material cannot be effectively shielded; the bottom layer is too thick and the planarization function cannot be increased further on the substrate, increasing the cost and risking cracking.
Referring to fig. 3, according to some embodiments of the present invention, an inorganic material layer 3 is further included between the base film layer 1 and the barrier layer 2. The inorganic material layer is formed of at least one of alumina, silica, iron oxide, zirconia, and silicon nitride, and can be formed by a method such as vapor deposition, sputtering, or PECVD. By arranging the inorganic material layer, the water and oxygen barrier property of the membrane material can be further improved.
According to some embodiments of the present invention, the thickness of the inorganic material layer may be 5 to 500nm, such as 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, and the like, and preferably 10 to 50 nm. The inventors found that if the thickness of the inorganic material layer is too small, the gas barrier property may not meet the use requirements; if the thickness of the inorganic material layer is too large, there is a possibility of cracking and a risk of deterioration of barrier properties during subsequent use.
Referring to fig. 4, according to some embodiments of the present invention, each of the barrier layer 2 and the inorganic material layer 3 may include a plurality and be alternately arranged in a thickness direction of the base film layer 1. When the structure design is adopted, the thickness of each inorganic material layer 2 is preferably 10 to 100nm, and the thickness of each barrier layer 3 is preferably 0.005 to 5 μm. In addition, it should be noted that the number of barrier layers and inorganic material layers in the actual product is not limited by fig. 4.
The coating method for forming the barrier layer by the aqueous coating solution is not particularly limited, and may be, for example, one of roll coating, gravure coating, blade coating, slot coating, extrusion coating, air knife coating, dip coating, and spray coating.
In addition, it should be noted that the gas barrier film has all the features and advantages described above for the aqueous coating solution, and thus, the details are not repeated herein.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
The gas barrier film was prepared according to the following procedure:
(1) adding 50g of PVA R-3109 into 950g of water, heating to 95 ℃, preserving the temperature for 1h, and stirring in the whole process to obtain a PVA solution 1 with the solid content of 5%.
(2) 28.8g of TEOS, 8g of methanol, 56g of 0.1mol/L hydrochloric acid aqueous solution and 55.7g of nano-silica dispersion (silica content 30 wt%, particle size 3nm) were mixed together and stirred at room temperature for 1 hour to obtain hydrolysate 1.
(3) The PVA solution 1, the hydrolysate 1 and 5g of silok8000 are added simultaneously and stirred for 24h to obtain a coating solution 1 with the solid content of 6.5 percent.
(4) A20 nm silicon oxide layer was deposited on 12 μm PET by PECVD method with a water permeability of 1.5 g.m-2·day-1Oxygen permeability of 2cc m-2·day-1. Coating the coating liquid on the barrier surface for 1, curing at 120 ℃ for 1min, and drying to the thickness of 500 nm.
Example 2
The gas barrier film was prepared according to the following procedure:
(1) PVA solution 1 was obtained according to the method of example 1.
(2) 1.7g of TEOS, 8g of methanol, 56g of methanol, 0.1mol/L hydrochloric acid aqueous solution and 81.7g of nano-silica dispersion (silica content 30 wt%, particle size 3nm) were mixed together and stirred at room temperature for 1 hour to obtain hydrolysate 2.
(3) The PVA solution 1, the hydrolysate 2 and 5g of silok8000 are added simultaneously and stirred for 24h to obtain a coating solution 2 with the solid content of 6.5 percent.
(4) A20 nm silicon oxide layer was deposited on 12 μm PET by PECVD method with a water permeability of 1.5 g.m-2·day-1Oxygen permeability of 2cc m-2·day-1. Coating liquid 2 on the barrier surface, curing at 120 ℃ for 1min, and drying to a thickness of 500 nm.
Example 3
The gas barrier film was prepared according to the following procedure:
(1) adding 5g of PVA R-3109 into 95g of water, heating to 95 ℃, preserving the temperature for 1h, and stirring in the whole process to obtain a PVA solution 2 with the solid content of 5%.
(2) 86.8g of TEOS, 8.6g of methanol, 60g of 0.1mol/L hydrochloric acid aqueous solution and 166.7g of nano-silica dispersion (the content of silica is 30 wt%, and the particle size is 3nm) are mixed together and stirred at room temperature for 1 hour to obtain hydrolysate 3.
(3) Mixing the PVA solution 2, the hydrolysate 3 and 808g of water, and simultaneously adding 5g of silok8000 and stirring for 24h to obtain a coating solution 3 with the solid content of 6.5 percent.
(4) A20 nm silicon oxide layer was deposited on 12 μm PET by PECVD method with a water permeability of 1.5 g.m-2·day-1Oxygen permeability of 2cc m-2·day-1. Coating the coating liquid on the barrier surface for 3 min at 120 ℃ and curing for 1min, wherein the coating layer is dried to 500 nm.
Example 4
The gas barrier film was prepared according to the following procedure:
(1) PVA solution 2 was obtained according to the method of example 2.
(2) 5.1g of TEOS, 8.6g of methanol, 60g of 0.1mol/L hydrochloric acid aqueous solution and 245g of nano-silica dispersion (the content of silica is 30 wt%, and the particle size is 3nm) are mixed together, and stirred at room temperature for 1 hour to obtain hydrolysate 4.
(3) The PVA solution 2, the hydrolysate 4, 811g of water, and 5g of silok8000 were mixed and stirred for 24 hours to obtain a coating solution 4 having a solid content of 6.5%.
(4) A20 nm silicon oxide layer was deposited on 12 μm PET by PECVD method with a water permeability of 1.5 g.m-2·day-1Oxygen permeability of 2cc m-2·day-1. Coating liquid 4 on the barrier surface, curing at 120 deg.C for 1min, and coating layer dry thickness 500 nm.
Example 5
The gas barrier film was prepared according to the following procedure:
(1) PVA solution 2 was obtained according to the method of example 2.
(2) 86.8g of TEOS, 8.6g of methanol, 60g of 0.1mol/L hydrochloric acid aqueous solution and 166.7g of nano-silica dispersion (the content of silica is 30 wt%, and the particle size is 50nm) are mixed together and stirred at room temperature for 1 hour to obtain hydrolysate 5.
(3) Mixing the PVA solution 2, the hydrolysate 5 and 808g of water, and simultaneously adding 5g of silok8000 and stirring for 24h to obtain a coating solution 5 with the solid content of 6.5 percent.
(4) A20 nm silicon oxide layer was deposited on 12 μm PET by PECVD method with a water permeability of 1.5 g.m-2·day-1Oxygen permeability of 2cc m-2·day-1. Coating liquid 5 on the barrier surface, curing at 120 deg.C for 1min, and coating layer dry thickness 500 nm.
Example 6
The gas barrier film was prepared according to the following procedure:
(1) adding 5g of PVA R-2105 into 95g of water, heating to 95 ℃, preserving the heat for 1h, and stirring in the whole process to obtain a PVA solution 3 with the solid content of 5%.
(2) Hydrolysate 3 was prepared according to the procedure of example 3.
(3) Mixing the PVA solution 3, the hydrolysate 3 and 808g of water, and simultaneously adding 5g of silok8000 and stirring for 24h to obtain a coating solution 6 with the solid content of 6.5 percent.
(4) A 20nm silicon oxide layer is deposited on 12 μm PET by PECVD method, and the water permeability is 1.5 g.m-2·day-1Oxygen permeability of 2cc m-2·day-1. Coating liquid 6 on the barrier surface, curing at 120 deg.C for 1min, and coating layer dry thickness 500 nm.
Example 7
The gas barrier film was prepared according to the following procedure:
(1) adding 5g of PVA P-6060 into 95g of water, heating to 95 ℃, preserving heat for 1h, and stirring in the whole process to obtain a PVA solution 4 with the solid content of 5%.
(2) Hydrolysate 3 was prepared according to the procedure of example 3.
(3) Mixing the PVA solution 4, the hydrolysate 3 and 808g of water, and simultaneously adding 5g of silok8000 and stirring for 24h to obtain a coating solution 7 with the solid content of 6.5 percent.
(4) A 20nm silicon oxide layer is deposited on 12 μm PET by PECVD method, and the water permeability is 1.5 g.m-2·day-1Oxygen permeability of 2cc m-2·day-1. Coating liquid 7 on the barrier surface, curing at 120 deg.C for 1min, and coating layer dry thickness 500 nm.
Example 8
The gas barrier film was prepared according to the following procedure:
(1) coating solution 7 was obtained in the same manner as in example 7.
(2) Coating a coating liquid 7 on one side of PET with the thickness of 12 mu m, curing for 2min at 120 ℃, and drying the coating to the thickness of 2 mu m to obtain the gas barrier film with the structure of the single-side coating barrier layer.
Example 9
The gas barrier film was prepared according to the following procedure:
(1) coating solution 7 was obtained in the same manner as in example 7.
(2) Coating the coating liquid 7 on two sides of the PET with the thickness of 12 mu m, curing for 2min at 120 ℃, and drying the coating with the thickness of 2 mu m to obtain the gas barrier film with the structure of the barrier layer coated on two sides.
Example 10
The gas barrier film was prepared according to the following procedure:
(1) the surface of the barrier layer of the gas barrier film obtained was prepared in the same manner as in example 1.
(2) The 15-micron PA film and the 60-micron CPP film are sequentially compounded by using the bi-component polyurethane adhesive, the total thickness of the adhesive is 4 microns, and the structure of the prepared packaging film is a barrier film// adhesive layer// PA film// adhesive layer// CPP film.
Example 11
The gas barrier film was prepared according to the following procedure:
(1) the surface of the barrier layer of the obtained gas barrier film was prepared in the same manner as in example 7.
(2) The 15-micron PA film and the 60-micron CPP film are sequentially compounded by using the bi-component polyurethane adhesive, the total thickness of the adhesive is 4 microns, and the structure of the prepared packaging film is a barrier film// adhesive layer// PA film// adhesive layer// CPP film.
Comparative example 1
The gas barrier film was prepared according to the following procedure:
(1) a20 nm silicon oxide layer was deposited on 12 μm PET by PECVD method with a water permeability of 1.5 g.m-2·day-1Oxygen permeability of 2cc m-2·day-1。
(2) A15-micron PA film and a 60-micron CPP film are sequentially compounded on silicon oxide by using a double-component polyurethane adhesive, the total thickness of the adhesive is 4 microns, and the prepared packaging film is of an inorganic material layer// adhesive layer// PA film// adhesive layer// CPP film structure.
Comparative example 2
The gas barrier film was prepared according to the following procedure:
(1) 50g of PVA103 is added into 950g of water, the temperature is raised to 95 ℃, the temperature is kept for 1h, and the PVA solution 5 with the solid content of 5 percent is obtained after the whole process of stirring.
(2) 28.8g of TEOS, 8g of methanol, 56g of 0.1mol/L hydrochloric acid aqueous solution and 55.7g of nano-silica dispersion (silica content 30 wt%, particle size 3nm) were mixed together and stirred at room temperature for 1 hour to obtain hydrolysate 1.
(3) The PVA solution 5, the hydrolysate 1 and 5g of silok8000 are added simultaneously and stirred for 24h to obtain a coating liquid 8 with the solid content of 6.5 percent.
(4) A20 nm silicon oxide layer was deposited on 12 μm PET by PECVD method with a water permeability of 1.5 g.m-2·day-1Oxygen permeability of 2cc m-2·day-1. Coating the coating liquid 8 on the barrier surface, curing at 120 ℃ for 1min, and drying to the thickness of 500 nm.
Comparative example 3
The gas barrier film was prepared according to the following procedure:
(1) adding 50g of PVA R-3109 into 950g of water, heating to 95 ℃, preserving the temperature for 1h, and stirring in the whole process to obtain a PVA solution 1 with the solid content of 5%.
(2) 66.7g of TEOS, 8g of methanol and 56g of 0.1mol/L hydrochloric acid aqueous solution are stirred for 1 hour at room temperature to obtain hydrolysate 6.
(3) The PVA solution 1, the hydrolysate 6 and 5g of silok8000 are added simultaneously and stirred for 24h to obtain a coating liquid 9 with the solid content of 6.5 percent.
(4) A20 nm silicon oxide layer was deposited on 12 μm PET by PECVD method with a water permeability of 1.5 g.m-2·day-1Oxygen permeability of 2cc m-2·day-1. Coating the coating liquid 9 on the barrier surface, curing at 120 ℃ for 1min, and drying to the thickness of 500 nm.
Comparative example 4
The gas barrier film was prepared according to the following procedure:
(1) adding 50g of PVA R-3109 into 950g of water, heating to 95 ℃, preserving the temperature for 1h, and stirring in the whole process to obtain a PVA solution 1 with the solid content of 5%.
(2) 83g of a nano-silica dispersion (silica content: 30 wt%, particle diameter: 3nm), 8g of methanol, and 56g of a 0.1mol/L hydrochloric acid aqueous solution were stirred at room temperature for 1 hour to obtain a mixed solution 1.
(3) PVA solution 1, mixed solution 1 and 5g silok8000 were simultaneously added and stirred for 24 hours to obtain coating solution 10 with a solid content of 6.5%.
(4) A20 nm silicon oxide layer was deposited on 12 μm PET by PECVD method with a water permeability of 1.5 g.m-2·day-1Oxygen permeability of 2cc m-2·day-1. Coating the coating liquid on the barrier surface for 10 min at 120 ℃ and curing for 1min, wherein the coating layer is dried to 500 nm.
Comparative example 5
The gas barrier film was prepared according to the following procedure:
(1) the surface of the barrier layer of the gas barrier film was prepared in accordance with the method of comparative example 2.
(2) The 15-micron PA film and the 60-micron CPP film are sequentially compounded by using the bi-component polyurethane adhesive, the total thickness of the adhesive is 4 microns, and the structure of the prepared packaging film is a barrier film// adhesive layer// PA film// adhesive layer// CPP film.
Comparative example 6
The gas barrier film was prepared according to the following procedure:
(1) the surface of the barrier layer of the gas barrier film was prepared in accordance with the method of comparative example 3.
(2) The 15-micron PA film and the 60-micron CPP film are sequentially compounded by using the bi-component polyurethane adhesive, the total thickness of the adhesive is 4 microns, and the structure of the prepared packaging film is a barrier film// adhesive layer// PA film// adhesive layer// CPP film.
Comparative example 7
The gas barrier film was prepared according to the following procedure:
(1) the surface of the barrier layer of the gas barrier film was prepared in accordance with the method of comparative example 4.
(2) The 15-micron PA film and the 60-micron CPP film are sequentially compounded by using the bi-component polyurethane adhesive, the total thickness of the adhesive is 4 microns, and the structure of the prepared packaging film is a barrier film// adhesive layer// PA film// adhesive layer// CPP film.
Test example 1
The stability of the coating solutions in the above examples and comparative examples was monitored as in table 1:
TABLE 1
Name (R) Gel time at room temperature
Example 1 Coating liquid 1 ≥7day
Example 2 Coating liquid 2 ≥7day
Example 3 Coating liquid 3 ≥7day
Example 4 Coating liquid 4 ≥7day
Example 5 Coating liquid 5 ≥7day
Example 6 Coating liquid 6 ≥7day
Example 7 Coating liquid7 ≥7day
Comparative example 2 Coating liquid 8 ≥7day
Comparative example 3 Coating liquid 9 ≥7day
Comparative example 4 Coating liquid 10 ≤3day
The test result shows that the aqueous coating liquid has better stability and can be stored for at least 7 days at room temperature. In comparative example 4, the large specific surface area of the nanoparticles resulted in poor stability of the coating liquid since no siloxane hydrolyzate was introduced.
Test example 2
The volume shrinkage during curing was characterized by comparing the degree of curling after the silicon oxide plating film on 12 μm PET was coated with each coating liquid, and the results are shown in table 2.
TABLE 2
Degree of curling of substrate
Example 1 Leveling
Example 2 Leveling
Example 3 Leveling
Example 4 Leveling
Example 5 Leveling
Example 6 Leveling
Example 7 Leveling
Comparative example 2 Leveling
Comparative example 3 Curling toward the barrier surface
Comparative example 4 Leveling
The test results showed that the volume shrinkage during the curing of the coating layer can be suppressed after the nanoparticles are introduced into the coating liquid, thereby obtaining a gas barrier film with good flatness, whereas in comparative example 3, the volume shrinkage during the curing of the coating layer causes the film material to curl toward the barrier surface because the nanoparticles are not introduced.
Test example 3
The composite films were subjected to a retort test at 121 ℃ for 40min, and the results of comparison of Oxygen Transmission Rates (OTR) before and after retort are shown in Table 3.
TABLE 3
Figure BDA0003168537920000131
The test results show that the oxygen transmission rate OTR before and after retort does not change much in the gas barrier films of example 10 and example 11 prepared according to the present invention. In comparative example 1, where the barrier layer of the present invention was not incorporated, the retort process resulted in damage to the silica layer, resulting in a significant increase in OTR. In comparative example 5, with conventional PVA103, no chemical bonding could be formed between the organic component and the inorganic component, and the barrier properties were also significantly deteriorated after cooking. In comparative example 6, no nanoparticles were introduced into the coating solution, and the inorganic layer was somewhat damaged by volume shrinkage during curing of the coating layer, resulting in a high OTR before steaming. In comparative example 7, only nanoparticles were introduced into the inorganic component, and no siloxane hydrolyzate was introduced, and effective bonding between the organic and inorganic components was also not possible, and the increase in OTR after cooking was also significant.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. An aqueous coating liquid, characterized by comprising: 100 parts of water-soluble polymer, 50-1500 parts of siloxane hydrolysate and nano oxide, 0.01-10 parts of assistant and 1000-12000 parts of solvent; wherein the weight ratio of the siloxane hydrolysate to the nano oxide is 1 (2.0-50).
2. The aqueous coating solution according to claim 1, wherein the water-soluble polymer is at least one of silane-modified polyvinyl alcohol, silane-modified starch, silane-modified cellulose, and silane-modified chitosan, and preferably is silane-modified polyvinyl alcohol.
3. The aqueous coating solution according to claim 2, wherein the silane-modified polyvinyl alcohol has a molar ratio of silane groups to hydroxyl groups of 0.5/99.5 to 5/95, a molecular weight of 1000 to 5000, and a degree of alcoholysis of 80 to 99.9%.
4. The aqueous coating solution according to claim 1, wherein the siloxane hydrolyzate is Si (OR)4Hydrolyzing under the condition that the pH value is less than or equal to 4 to obtain a product, wherein R is C1-8An alkyl group.
5. The aqueous coating solution according to claim 1, wherein the nano oxide is at least one selected from the group consisting of alumina, silica, zinc oxide, titanium oxide, zirconia, magnesium carbonate, calcium carbonate and barium sulfate, and has an average particle diameter of 1 to 100 nm.
6. The aqueous coating solution according to claim 1, wherein the auxiliary agent is at least one selected from the group consisting of a wetting agent, a coupling agent, an adhesion promoter, and a leveling agent.
7. The aqueous coating solution according to claim 1, wherein the solvent is a mixed solvent of water and an alcohol.
8. A gas barrier film, comprising: a base film layer and a barrier layer formed on one or both surfaces of the base film layer, the barrier layer being formed from the aqueous coating liquid according to any one of claims 1 to 7;
optionally, the thickness of the barrier layer is 0.05-5 μm.
9. The gas barrier film of claim 8, wherein the base film layer is a polyolefin-based film, a polyester-based film, or a polyamide-based film.
10. The gas barrier film of claim 8, further comprising an inorganic material layer between the base film layer and the barrier layer;
optionally, the inorganic material layer is formed of at least one of alumina, silica, iron oxide, zirconia, and silicon nitride;
optionally, the thickness of the inorganic material layer is 5-500 nm;
optionally, each of the barrier layers and the inorganic material layer includes a plurality of layers and is alternately arranged in a thickness direction of the base film layer.
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CN115873458A (en) * 2023-01-03 2023-03-31 中国乐凯集团有限公司 Aqueous coating liquid, method for producing same, and gas barrier film
WO2023155380A1 (en) * 2022-02-18 2023-08-24 苏州赛伍应用技术股份有限公司 Water vapor barrier coating solution and preparation method therefor, and water vapor barrier coating

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CN109266123A (en) * 2018-08-23 2019-01-25 中国乐凯集团有限公司 A kind of aqueous high-obstructing coating liquid and its high-isolation film
CN110305540A (en) * 2019-07-04 2019-10-08 中国乐凯集团有限公司 A kind of aqueous high-obstructing coating liquid and preparation method thereof

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CN109266123A (en) * 2018-08-23 2019-01-25 中国乐凯集团有限公司 A kind of aqueous high-obstructing coating liquid and its high-isolation film
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Application publication date: 20211109