WO2022205720A1 - Special polyvinyl alcohol emulsion for protective coating for aluminum oxide-coated film, and preparation method for and application of polyvinyl alcohol emulsion - Google Patents

Special polyvinyl alcohol emulsion for protective coating for aluminum oxide-coated film, and preparation method for and application of polyvinyl alcohol emulsion Download PDF

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WO2022205720A1
WO2022205720A1 PCT/CN2021/110174 CN2021110174W WO2022205720A1 WO 2022205720 A1 WO2022205720 A1 WO 2022205720A1 CN 2021110174 W CN2021110174 W CN 2021110174W WO 2022205720 A1 WO2022205720 A1 WO 2022205720A1
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polyvinyl alcohol
protective coating
aluminum oxide
special
alcohol emulsion
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PCT/CN2021/110174
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French (fr)
Chinese (zh)
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朱清梅
袁业兴
黄宏存
陈招强
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海南必凯水性新材料有限公司
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Publication of WO2022205720A1 publication Critical patent/WO2022205720A1/en

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a special polyvinyl alcohol emulsion for a protective coating of an aluminum oxide film, a preparation method and application thereof.
  • Alumina-coated film is one of the high-barrier packaging materials in the world at present, with good transparency, excellent oxygen barrier, moisture barrier and other properties, and its barrier properties will not change under high temperature and high humidity environment, and its adaptability to atmospheric environment is excellent. , With microwave penetration and environmental protection, it is widely used in the packaging of food, beverages, meat products, condiments, medicine and other fields.
  • Polyvinyl alcohol is a polyhydroxy polymer with good water solubility and film-forming properties under the appropriate alcoholysis degree. Due to its intermolecular hydrogen bonding, the coating can protect alumina in a dry environment. Moreover, polyvinyl alcohol has no pollution to the environment, and has been applied as an ideal protective coating.
  • Chinese patent CN104354362A uses polyvinyl alcohol as a protective coating. Although this technology has a certain protective effect on the aluminum oxide film, if the aluminum oxide film made is used for packaging meat products and cooked food, it will be exposed to high temperature. After retorting and sterilization (121°C, 45min), the polyvinyl alcohol coating will turn white in the presence of hot water, which limits the application of aluminum oxide film to a certain extent.
  • the technical problem to be solved by the present invention is to provide a special polyvinyl alcohol emulsion for aluminum oxide film protective coating, its preparation method and application, and the polyvinyl alcohol emulsion of the present invention is used for aluminum oxide film protective coating. , the performance of the obtained aluminum oxide film is better.
  • the invention provides a special polyvinyl alcohol emulsion for the protective coating of aluminum oxide film, which is prepared by dissolving and emulsification of raw materials comprising the following components:
  • the degree of polymerization of the polyvinyl alcohol is 400-1900, and the degree of alcoholysis is 88%-99%.
  • the particle size of the kaolin is 20-100 nm.
  • the dispersant is selected from sodium polyacrylate and/or sodium hexametaphosphate
  • the crosslinking agent is di-tert-butyl peroxide.
  • the defoamer is ethanol and/or isopropanol.
  • the present invention also provides a preparation method of the above-mentioned special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film, comprising the following steps:
  • step C) subjecting the product after the modification reaction in step B), the crosslinking agent and the defoaming agent to a crosslinking reaction to obtain a special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film.
  • the temperature of heating and dissolving is 90-95°C, and the time is 2-3h;
  • the heating and dissolving are carried out in stirring, and the stirring speed is 100-150 r/min.
  • step B) before carrying out the modification reaction of the polyvinyl alcohol solution, kaolin, dispersant and formamide, it also includes:
  • the temperature of the modification reaction is 75-80° C., and the time is 1-2 h.
  • step C) before carrying out the cross-linking reaction of the product after the modification reaction in step B), the cross-linking agent and the defoaming agent, it also includes:
  • the temperature of the cross-linking reaction is 50-60° C., and the time is 1-2 h;
  • the cross-linking reaction is carried out under stirring, and the stirring speed is 50-100 r/min.
  • the present invention also provides an aluminum oxide coating film containing a protective coating, comprising:
  • the protective coating is formed from the above-mentioned special polyvinyl alcohol emulsion for the aluminum-plated film protective coating, or the protective coating is special for the aluminum-plated thin-film protective coating prepared by the above-mentioned preparation method.
  • a polyvinyl alcohol emulsion is formed.
  • the invention provides a special polyvinyl alcohol emulsion for a protective coating of an aluminum oxide plated film, which is prepared from raw materials comprising the following components: polyvinyl alcohol 8wt%-15wt%; soft water 78wt%-87wt%; kaolin 3wt%-5wt% %; dispersant 0.1wt% ⁇ 0.5wt%; formamide 1wt% ⁇ 3wt%; crosslinking agent 1wt% ⁇ 3wt%; defoamer 0.05wt% ⁇ 0.1wt%; the sum of the above components is 100 %.
  • the kaolin is dispersed in the polyvinyl alcohol emulsion under the action of the dispersant, and under the action of the formamide through its own group, Shield the hydroxyl group in the polyvinyl alcohol molecule and reduce its affinity with water.
  • the linear molecules of polyvinyl alcohol are connected to each other to form a network structure, which improves the adhesion between the coating and the substrate film.
  • the foam can be eliminated by adding an appropriate amount of defoaming agent, and at the same time, the surface tension of the emulsion system can be adjusted to facilitate better coating applications.
  • the kaolin molecules are precipitated on the surface of the coating in a micro-flaky structure, which effectively improves the crack resistance and damage resistance of the aluminum oxide substrate film, and also avoids hot water to polymerize.
  • the destruction of the vinyl alcohol coating ensures that the appearance of the film remains transparent after high-temperature retort sterilization (121°C, 45min).
  • the polyvinyl alcohol emulsion of the present invention is used for the protective coating of the aluminum oxide film, and the various components in the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film work synergistically, and the overall performance of the finally obtained aluminum oxide film is better than that of the aluminum oxide film. excellent.
  • the protective coating is prepared by using the special polyvinyl alcohol emulsion for the protective coating of the alumina-plated film of the present invention, which overcomes the defect that the conventional polyvinyl alcohol is used as the alumina-plated protective coating and has a whitish appearance after moist heat sterilization, and broadens the scope of the alumina-plated film. Application in the field of packaging.
  • the invention provides a special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film, which is prepared from the raw materials comprising the following components:
  • the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention is prepared by dissolving and emulsification of the raw materials including the above-mentioned components.
  • the preparation raw materials of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention include polyvinyl alcohol.
  • the content of the polyvinyl alcohol in the preparation raw material is 8 wt %, 15 wt %, 10 wt %, 9 wt % or 13 wt %.
  • the degree of polymerization of the polyvinyl alcohol is 400-1900, and the degree of alcoholysis is 88%-99%.
  • the preparation raw materials of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also include soft water.
  • the content of the soft water in the preparation raw material is 82 wt %, 78 wt %, 81 wt % or 80 wt %.
  • the soft water can be prepared by resin exchange.
  • the method of the resin exchange is not particularly limited in the present invention, and the resin exchange method well known to those skilled in the art can be used.
  • the raw material for preparing the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also includes kaolin.
  • the content of the kaolin clay in the preparation raw material is 4 wt %, 3 wt %, 4.5 wt %, 5 wt % or 3.4 wt %.
  • the particle size of the kaolin is 20-100 nm.
  • the preparation raw material of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also includes a dispersant.
  • the content of the dispersant in the preparation raw material is 0.5 wt %, 0.25 wt %, 0.4 wt %, 0.32 wt % or 0.1 wt %.
  • the dispersing agent is selected from sodium polyacrylate and/or sodium hexametaphosphate.
  • the preparation raw material of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also includes formamide.
  • the content of the formamide in the preparation raw material is 2.4 wt %, 2.7 wt %, 1.03 wt %, 3 wt % or 1 wt %.
  • the preparation raw material of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also includes a crosslinking agent.
  • the content of the cross-linking agent in the preparation raw material is 3 wt %, 1 wt %, 2.6 wt % or 1.44 wt %.
  • the crosslinking agent is di-tert-butyl peroxide.
  • the preparation raw materials of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also include a defoamer.
  • the content of the defoaming agent in the preparation raw material is 0.1 wt %, 0.05 wt %, 0.07 wt %, 0.08 wt % or 0.06 wt %.
  • the antifoaming agent is ethanol and/or isopropanol.
  • the present invention also provides a preparation method of the above-mentioned special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film, comprising the following steps:
  • step C) carry out cross-linking reaction with the product after step B) modification reaction, cross-linking agent and defoamer, obtain the special-purpose polyvinyl alcohol emulsion of aluminum oxide film protective coating.
  • soft water and polyvinyl alcohol are heated and dissolved to obtain a polyvinyl alcohol solution.
  • the temperature of the heating and dissolving is 90-95° C., and the time is 2-3 hours. In certain embodiments, the temperature for heating and dissolving is 95°C, 93°C, 90°C or 91°C. In some embodiments, the heating and dissolving time is 3h. In some embodiments of the present invention, the heating and dissolving are performed in stirring, and the stirring speed is 100-150 r/min. In certain embodiments, the rotational speed of the stirring is 150 r/min, 140 r/min, 130 r/min or 100 r/min.
  • the polyvinyl alcohol solution After the polyvinyl alcohol solution is obtained, the polyvinyl alcohol solution, kaolin, dispersant and formamide are subjected to a modification reaction.
  • the polyvinyl alcohol solution was cooled to 75-80°C.
  • the temperature product of cooling the polyvinyl alcohol solution is the temperature of the modification reaction.
  • the temperature of the modification reaction is 75-80° C., and the time is 1-2 h. In certain embodiments, the temperature of the modification reaction is 80°C, 75°C, 79°C, or 78°C. In certain embodiments, the modification reaction time is 1 h.
  • the product after the modification reaction, the crosslinking agent and the defoaming agent are subjected to a crosslinking reaction to obtain a special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film.
  • the cross-linking agent and the defoaming agent before the product after the modification reaction, the cross-linking agent and the defoaming agent are subjected to the cross-linking reaction, it also includes:
  • the product after the modification reaction is cooled to 50-60°C.
  • the temperature after cooling the product after the modification reaction is the temperature of the crosslinking reaction.
  • the temperature of the cross-linking reaction is 50-60° C., and the time is 1-2 h. In certain embodiments, the temperature of the crosslinking reaction is 60°C, 50°C, 55°C, or 58°C. In certain embodiments, the time of the crosslinking reaction is 1 h, 1.5 h, 2 h, 1.4 h or 1.6 h. In some embodiments of the present invention, the cross-linking reaction is carried out under stirring, and the stirring speed is 50-100 r/min. In certain embodiments, the rotational speed of the stirring is 50 r/min, 80 r/min, 70 r/min, 100 r/min or 90 r/min.
  • the method further includes standing and cooling. In certain embodiments of the invention, cooling to room temperature.
  • the present invention also provides an aluminum oxide coating film containing a protective coating, comprising:
  • the protective coating is formed from the above-mentioned special polyvinyl alcohol emulsion for the aluminum-plated film protective coating, or the protective coating is special for the aluminum-plated thin-film protective coating prepared by the above-mentioned preparation method.
  • a polyvinyl alcohol emulsion is formed.
  • the present invention has no special limitation on the type and source of the alumina substrate film.
  • the alumina substrate film can be prepared according to the preparation method described in Chinese Patent CN108570644A.
  • the alumina substrate film is prepared according to the following method:
  • the vacuum degree reaches 5 ⁇ 10 -4 MPa or more
  • the aluminum wire is melted and evaporated at 1600-1800 °C, and at the same time, high-purity oxygen with a purity of 95%-99% is introduced to form the surface of the substrate film.
  • Alumina layer was obtained to obtain an alumina base film.
  • the preparation of the alumina substrate film is performed in a vacuum chamber.
  • the melting and evaporation of the aluminum wire is performed in an evaporation boat.
  • the introduction of high-purity oxygen can make aluminum vapor react with oxygen to form aluminum oxide, which is deposited on the surface of the substrate film, and after cooling, the aluminum oxide substrate film can be obtained.
  • the material of the substrate film can be selected from PET.
  • the thickness of the substrate film is 12-14 ⁇ m.
  • the thickness of the substrate film is 12 ⁇ m PET, 13 ⁇ m PET, or 14 ⁇ m PET.
  • the aluminum oxide layer has a thickness of 0.01-0.03 ⁇ m.
  • the aluminum oxide layer has a thickness of 0.01 ⁇ m, 0.03 ⁇ m, or 0.02 ⁇ m.
  • the thickness of the protective coating is 0.3-0.5 ⁇ m. In certain embodiments, the protective coating has a thickness of 0.3 ⁇ m, 0.5 ⁇ m, 0.4 ⁇ m, 0.45 ⁇ m, or 0.35 ⁇ m.
  • the aluminum oxide-coated film containing the protective coating is prepared according to the following method:
  • a protective emulsion is applied on the surface of the aluminum oxide substrate film by a reverse kiss coating method, and after drying, a protective coating is formed on the surface of the aluminum oxide substrate film to obtain an aluminum oxide plated film coated with the protective coating;
  • the protective emulsion is the above-mentioned special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film, or the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film prepared by the above-mentioned preparation method.
  • the parameters of the coating roll of the coating are 120-150 meshes. In certain embodiments, the coating roll parameters are 120 mesh, 130 mesh, 140 mesh, 150 mesh or 145 mesh.
  • the drying temperature is 90-110°C. In certain embodiments, the drying temperature is 90°C, 100°C, 110°C, 105°C or 95°C. In some embodiments, the drying adopts hot air drying.
  • the coating weight of the coating is 0.3-0.5 g/m 2 . In certain embodiments, the coating weight is 0.3 g/m 2 , 0.5 g/m 2 , 0.4 g/m 2 , 0.45 g/m 2 or 0.35 g/m 2 .
  • the present invention has no special limitation on the source of the raw materials used above, and can be generally commercially available.
  • the kaolin is dispersed in the polyvinyl alcohol emulsion under the action of the dispersant, and under the action of the formamide through its own group, Shield the hydroxyl group in the polyvinyl alcohol molecule and reduce its affinity with water.
  • the linear molecules of polyvinyl alcohol are connected to each other to form a network structure, which improves the adhesion between the coating and the substrate film.
  • the foam can be eliminated by adding an appropriate amount of defoaming agent, and at the same time, the surface tension of the emulsion system can be adjusted to facilitate better coating applications.
  • the kaolin molecules are precipitated on the surface of the coating in a micro-flaky structure, which effectively improves the crack resistance and damage resistance of the aluminum oxide substrate film, and also avoids hot water to polymerize.
  • the destruction of the vinyl alcohol coating ensures that the appearance of the film remains transparent after high-temperature retort sterilization (121°C, 45min).
  • the polyvinyl alcohol emulsion of the present invention is used for the protective coating of the aluminum oxide film, and the various components in the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film work synergistically, and the overall performance of the finally obtained aluminum oxide film is better than that of the aluminum oxide film. excellent.
  • the protective coating is prepared by using the special polyvinyl alcohol emulsion for the protective coating of the alumina-plated film of the present invention, which overcomes the defect that the conventional polyvinyl alcohol is used as the alumina-plated protective coating and has a whitish appearance after moist heat sterilization, and broadens the scope of the alumina-plated film. Application in the field of packaging.
  • the oxygen transmission rate of the aluminum oxide film is detected according to the standard GB/T 1038; the water vapor transmission rate of the aluminum oxide film is detected according to the standard GB/T 1037; according to the standard BB/T 0003- In 1994, the appearance of the alumina-plated film after being sterilized by high-temperature cooking (121°C, 45min) was tested.
  • the raw materials for the preparation of polyvinyl alcohol emulsion include:
  • the degree of polymerization of the polyvinyl alcohol is 400, and the degree of alcoholysis is 99%;
  • the particle size of the kaolin is 20-100 nm
  • the dispersant is sodium polyacrylate
  • the crosslinking agent is di-tert-butyl peroxide
  • the defoamer is ethanol.
  • Preparation methods include:
  • the 12 ⁇ m-thick roll PET substrate film placed in a vacuum chamber, close the vacuum chamber and evacuate.
  • the vacuum degree reaches 5 ⁇ 10 -4 MPa or more
  • the evaporation boat is heated to 1600°C, and then the purity is 95%.
  • the aluminum wire is continuously sent to the evaporation boat, so that the aluminum wire is continuously melted and evaporated on the evaporation boat, and at the same time, high-purity oxygen with a purity of 95% is introduced, and the aluminum vapor reacts with the oxygen to form alumina, which moves to the surface of the film After cooling, an alumina layer of 0.01 ⁇ m was formed on the surface of the base film to obtain an alumina base film.
  • the polyvinyl alcohol emulsion was coated on the surface of the alumina substrate film by reverse kiss coating, the parameters of the coating roller were 120 mesh, the coating weight was 0.3 g/m 2 , the thickness was 0.3 ⁇ m, and the oven temperature was The temperature is 90° C., and after being dried by hot air, a protective coating is formed on the surface of the alumina substrate film to obtain an alumina-plated film containing the protective coating.
  • the oxygen transmission rate, water vapor transmission rate and high temperature cooking (121°C, 45min) after sterilization of the aluminum oxide film with protective coating were tested.
  • the experimental results show that the aluminum oxide film with protective coating
  • the oxygen transmission rate is 0.6cc/m 2 ⁇ day
  • the water vapor transmission rate is 0.9g/m 2 ⁇ day
  • the appearance is transparent after being sterilized by high temperature cooking (121°C, 45min).
  • the raw materials for the preparation of polyvinyl alcohol emulsion include:
  • the degree of polymerization of the polyvinyl alcohol is 1900, and the degree of alcoholysis is 88%;
  • the particle size of the kaolin is 20-100 nm
  • Described dispersant is sodium hexametaphosphate
  • the crosslinking agent is di-tert-butyl peroxide
  • the defoamer is isopropanol.
  • Preparation methods include:
  • the evaporation boat Place the 13 ⁇ m-thick roll PET substrate film in a vacuum chamber, close the vacuum chamber and evacuate.
  • the vacuum degree reaches 5 ⁇ 10 -4 MPa or more
  • the evaporation boat is heated to 1650°C, and then the purity is 96%.
  • the aluminum wire is continuously sent to the evaporation boat, so that the aluminum wire is continuously melted and evaporated on the evaporation boat, and at the same time, high-purity oxygen with a purity of 96% is introduced, and the aluminum vapor and oxygen react to form alumina, which moves to the surface of the film After cooling, an alumina layer of 0.03 ⁇ m was formed on the surface of the base film to obtain an alumina base film.
  • the polyvinyl alcohol emulsion was coated on the surface of the alumina substrate film by reverse kiss coating, the coating roll parameter was 130 mesh, the coating weight was 0.5 g/m 2 , the thickness was 0.5 ⁇ m, and the oven temperature was The temperature is 100° C., and after being dried by hot air, a protective coating is formed on the surface of the alumina substrate film to obtain an alumina-plated film containing the protective coating.
  • the oxygen transmission rate, water vapor transmission rate and high temperature cooking (121°C, 45min) after sterilization of the aluminum oxide film with protective coating were tested.
  • the experimental results show that the aluminum oxide film with protective coating
  • the oxygen transmission rate is 1.0cc/m 2 ⁇ day
  • the water vapor transmission rate is 0.8g/m 2 ⁇ day
  • the appearance is transparent after being sterilized by high temperature cooking (121°C, 45min).
  • the raw materials for the preparation of polyvinyl alcohol emulsion include:
  • the degree of polymerization of the polyvinyl alcohol is 500, and the degree of alcoholysis is 90%;
  • the particle size of the kaolin is 20-100 nm
  • the dispersant is sodium polyacrylate
  • the crosslinking agent is di-tert-butyl peroxide
  • the defoamer is ethanol.
  • Preparation methods include:
  • the polyvinyl alcohol emulsion was coated on the surface of the alumina substrate film by reverse kiss coating, the coating roll parameter was 140 mesh, the coating weight was 0.4 g/m 2 , the thickness was 0.4 ⁇ m, and the oven temperature was The temperature is 110° C., and after drying with hot air, a protective coating is formed on the surface of the aluminum oxide base film to obtain an aluminum oxide plated film containing the protective coating.
  • the oxygen transmission rate, water vapor transmission rate and high temperature cooking (121°C, 45min) after sterilization of the aluminum oxide film with protective coating were tested.
  • the experimental results show that the aluminum oxide film with protective coating
  • the oxygen transmission rate is 0.7cc/m 2 ⁇ day
  • the water vapor transmission rate is 1.0g/m 2 ⁇ day
  • the appearance is transparent after being sterilized by high temperature cooking (121°C, 45min).
  • the raw materials for the preparation of polyvinyl alcohol emulsion include:
  • the degree of polymerization of the polyvinyl alcohol is 1700, and the degree of alcoholysis is 95%;
  • the particle size of the kaolin is 20-100 nm
  • Described dispersant is sodium hexametaphosphate
  • the crosslinking agent is di-tert-butyl peroxide
  • the defoamer is isopropanol.
  • Preparation methods include:
  • the evaporation boat Place the 13 ⁇ m-thick roll PET substrate film in a vacuum chamber, close the vacuum chamber and evacuate, when the vacuum degree reaches 5 ⁇ 10 -4 MPa or more, the evaporation boat is heated to 1750°C, and then the purity is 98%.
  • the aluminum wire is continuously sent to the evaporation boat, so that the aluminum wire is continuously melted and evaporated on the evaporation boat, and at the same time, high-purity oxygen with a purity of 98% is introduced, and the aluminum vapor and oxygen react to form alumina, which moves to the surface of the film After cooling, an alumina layer of 0.03 ⁇ m was formed on the surface of the base film to obtain an alumina base film.
  • the polyvinyl alcohol emulsion was coated on the surface of the alumina substrate film by reverse kiss coating.
  • the parameters of the coating roller were 150 mesh, the coating weight was 0.45 g/m 2 , the thickness was 0.45 ⁇ m, and the oven temperature was 0.45 ⁇ m.
  • the temperature is 105° C., and after being dried by hot air, a protective coating is formed on the surface of the alumina substrate film to obtain an alumina-plated film containing the protective coating.
  • the oxygen transmission rate, water vapor transmission rate and high temperature cooking (121°C, 45min) after sterilization of the aluminum oxide film with protective coating were tested.
  • the experimental results show that the aluminum oxide film with protective coating
  • the oxygen transmission rate is 0.6cc/m 2 ⁇ day
  • the water vapor transmission rate is 0.5g/m 2 ⁇ day
  • the appearance is transparent after being sterilized by high temperature cooking (121°C, 45min).
  • the raw materials for the preparation of polyvinyl alcohol emulsion include:
  • the degree of polymerization of the polyvinyl alcohol is 1500, and the degree of alcoholysis is 93%;
  • the particle size of the kaolin is 20-100 nm
  • the dispersant is sodium polyacrylate
  • the crosslinking agent is di-tert-butyl peroxide
  • the defoamer is ethanol.
  • Preparation methods include:
  • the polyvinyl alcohol emulsion was coated on the surface of the alumina substrate film by reverse kiss coating.
  • the parameters of the coating roller were 145 mesh, the coating weight was 0.35 g/m 2 , the thickness was 0.35 ⁇ m, and the oven temperature was 0.35 ⁇ m.
  • the temperature is 95° C., and after being dried by hot air, a protective coating is formed on the surface of the alumina substrate film to obtain an alumina-plated film containing the protective coating.
  • the oxygen transmission rate, water vapor transmission rate and high temperature cooking (121°C, 45min) after sterilization of the aluminum oxide film with protective coating were tested.
  • the experimental results show that the aluminum oxide film with protective coating
  • the oxygen transmission rate is 0.5cc/m 2 ⁇ day
  • the water vapor transmission rate is 0.8g/m 2 ⁇ day
  • the appearance is transparent after being sterilized by high temperature cooking (121°C, 45min).
  • Example 1 of CN102277049A The emulsion obtained in Example 1 of CN102277049A was coated on the surface of the alumina substrate film by reverse kiss coating, the coating roll parameter was 130 mesh, the coating weight was 0.5 g/m2, the thickness was 0.5 ⁇ m, and the oven The temperature is 100° C., and after being dried by hot air, a protective coating is formed on the surface of the aluminum oxide substrate film, and an aluminum oxide plated film containing the protective coating is obtained.
  • the oxygen transmission rate, water vapor transmission rate and high temperature cooking (121°C, 45min) after sterilization of the aluminum oxide film with protective coating were tested.
  • the experimental results show that the aluminum oxide film with protective coating
  • the oxygen transmission rate is 5cc/m 2 ⁇ day
  • the water vapor transmission rate is 8g/m 2 ⁇ day
  • the appearance turns white after being sterilized by high temperature cooking (121°C, 45min).

Abstract

The present invention relates to the technical field of polymer materials, in particular, to a special polyvinyl alcohol emulsion for a protective coating for an aluminum oxide-coated film, and a preparation method for and an application of the polyvinyl alcohol emulsion. The polyvinyl alcohol emulsion is prepared from raw materials comprising the following components: polyvinyl alcohol: 8-15 wt%; soft water: 78-87 wt%; kaolin: 3-5 wt%; a dispersant: 0.1-0.5 wt%; formamide: 1-3 wt%; a cross-linking agent: 1-3 wt%; a defoaming agent: 0.05-0.1 wt%, wherein the sum of the amounts of the above components is 100%. The polyvinyl alcohol emulsion in the present invention is used for a protective coating for an aluminum oxide-coated film, the components in the special polyvinyl alcohol emulsion for a protective coating for an aluminum oxide-coated film achieve a synergistic effect, and the comprehensive performance of a finally obtained aluminum oxide-coated film is excellent.

Description

镀氧化铝薄膜保护涂层专用聚乙烯醇乳液、其制备方法及应用Special polyvinyl alcohol emulsion for aluminum oxide film protective coating, its preparation method and application
本申请要求于2021年3月31日提交中国专利局、申请号为202110349737.4、发明名称为“镀氧化铝薄膜保护涂层专用聚乙烯醇乳液、其制备方法及应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on March 31, 2021 with the application number 202110349737.4 and the invention titled "Polyvinyl alcohol emulsion for aluminum oxide film protective coating, its preparation method and application" , the entire contents of which are incorporated herein by reference.
技术领域technical field
本发明涉及高分子材料技术领域，尤其涉及一种镀氧化铝薄膜保护涂层专用聚乙烯醇乳液、其制备方法及应用。The invention relates to the technical field of polymer materials, in particular to a special polyvinyl alcohol emulsion for a protective coating of an aluminum oxide film, a preparation method and application thereof.
背景技术Background technique
镀氧化铝薄膜是目前世界上高阻隔性包装材料之一，透明性好，阻氧、阻湿等性能非常优异，且在高温高湿环境下其阻隔性能不会发生改变，大气环境适应性优良，具有微波穿透性和环保性，因而广泛应用于食品、饮料、肉制品、调味品、医药等多个领域的包装。Alumina-coated film is one of the high-barrier packaging materials in the world at present, with good transparency, excellent oxygen barrier, moisture barrier and other properties, and its barrier properties will not change under high temperature and high humidity environment, and its adaptability to atmospheric environment is excellent. , With microwave penetration and environmental protection, it is widely used in the packaging of food, beverages, meat products, condiments, medicine and other fields.
但经过实验证明，镀镀氧化铝薄膜易龟裂，容易被损伤。在实际应用中，一般都需要在镀镀氧化铝薄膜上涂布一层涂层进行保护，使其在进行印刷和加工时不会遭到损伤。中国专利CN104371439A公开了一种自粘性PVDC乳液涂布的镀镀氧化铝薄膜及其制造方法，该技术是在镀氧化铝薄膜上涂布PVDC涂层，起到保护氧化铝作用，而且还改善了印刷性能。但是涂布PVDC涂层后，镀氧化铝薄膜不仅不能回收再生利用，而且还会使与其复合的其他本来可以回收再生利用的薄膜(如PE、CPP等)也不能回收再利用；废弃物在焚烧时还会产生氯化氢、二恶英等对人体和周围环境有毒、有害的物质。目前欧美等国家已经通过其它环保材料替代PVDC涂层。However, it has been proved by experiments that the plated aluminum oxide film is easy to crack and easily damaged. In practical applications, it is generally necessary to coat a layer of coating on the plated aluminum oxide film to protect it from damage during printing and processing. Chinese patent CN104371439A discloses a self-adhesive PVDC emulsion coated aluminum oxide film and its manufacturing method. The technology is to coat the PVDC coating on the aluminum oxide film to protect the aluminum oxide and improve the printing performance. However, after the PVDC coating is applied, the aluminum oxide film can not only be recycled and reused, but also other films that can be recycled and reused (such as PE, CPP, etc.) can not be recycled and reused; the waste is incinerated. It will also produce hydrogen chloride, dioxins and other toxic and harmful substances to the human body and the surrounding environment. At present, countries such as Europe and the United States have replaced PVDC coatings with other environmentally friendly materials.
聚乙烯醇是一种多羟基聚合物，在适当的醇解度下具有良好的水溶性和成膜性。由于其分子间氢键的作用,在干燥的环境下涂层可以对氧化铝起到保护作用。而且聚乙烯醇对环境无污染，作为一种理想的保护涂层已经得到应用。如中国专利CN104354362A涉及的采用聚乙烯醇作为保护涂层，虽然该技术对镀氧化铝薄膜起到了一定的保护作用，但是做出来的镀氧化铝薄膜若用于包装 肉制品和熟食时，在高温蒸煮杀菌(121℃，45min)后，该聚乙烯醇涂层遇到热水就会导致薄膜外观发白，从而在一定程度上限制了镀氧化铝薄膜的应用。Polyvinyl alcohol is a polyhydroxy polymer with good water solubility and film-forming properties under the appropriate alcoholysis degree. Due to its intermolecular hydrogen bonding, the coating can protect alumina in a dry environment. Moreover, polyvinyl alcohol has no pollution to the environment, and has been applied as an ideal protective coating. For example, Chinese patent CN104354362A uses polyvinyl alcohol as a protective coating. Although this technology has a certain protective effect on the aluminum oxide film, if the aluminum oxide film made is used for packaging meat products and cooked food, it will be exposed to high temperature. After retorting and sterilization (121°C, 45min), the polyvinyl alcohol coating will turn white in the presence of hot water, which limits the application of aluminum oxide film to a certain extent.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明要解决的技术问题在于提供一种镀氧化铝薄膜保护涂层专用聚乙烯醇乳液、其制备方法及应用，将本发明聚乙烯醇乳液用于镀氧化铝薄膜保护涂层，得到的镀氧化铝薄膜的性能较优。In view of this, the technical problem to be solved by the present invention is to provide a special polyvinyl alcohol emulsion for aluminum oxide film protective coating, its preparation method and application, and the polyvinyl alcohol emulsion of the present invention is used for aluminum oxide film protective coating. , the performance of the obtained aluminum oxide film is better.
本发明提供了一种镀氧化铝薄膜保护涂层专用聚乙烯醇乳液，由包括以下组分的原料经过溶解乳化制备得到：The invention provides a special polyvinyl alcohol emulsion for the protective coating of aluminum oxide film, which is prepared by dissolving and emulsification of raw materials comprising the following components:
Figure PCTCN2021110174-appb-000001
Figure PCTCN2021110174-appb-000001
以上各组分的用量之和为100％。The sum of the amounts of the above components is 100%.
优选的，所述聚乙烯醇的聚合度为400～1900，醇解度为88％～99％。Preferably, the degree of polymerization of the polyvinyl alcohol is 400-1900, and the degree of alcoholysis is 88%-99%.
优选的，所述高岭土的粒径为20～100nm。Preferably, the particle size of the kaolin is 20-100 nm.
优选的，所述的分散剂选自聚丙烯酸钠和/或六偏磷酸钠；Preferably, the dispersant is selected from sodium polyacrylate and/or sodium hexametaphosphate;
所述交联剂为二叔丁基过氧化物。The crosslinking agent is di-tert-butyl peroxide.
优选的，所述消泡剂为乙醇和/或异丙醇。Preferably, the defoamer is ethanol and/or isopropanol.
本发明还提供了一种上文所述的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液的制备方法，包括以下步骤：The present invention also provides a preparation method of the above-mentioned special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film, comprising the following steps:
A)将软水和聚乙烯醇加热溶解，得到聚乙烯醇溶液；A) heating and dissolving soft water and polyvinyl alcohol to obtain polyvinyl alcohol solution;
B)将所述聚乙烯醇溶液、高岭土、分散剂和甲酰胺进行改性反应；B) carrying out modification reaction with described polyvinyl alcohol solution, kaolin, dispersant and formamide;
C)将步骤B)改性反应后的产物、交联剂和消泡剂进行交联反应，得到镀氧化铝薄膜保护涂层专用聚乙烯醇乳液。C) subjecting the product after the modification reaction in step B), the crosslinking agent and the defoaming agent to a crosslinking reaction to obtain a special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film.
优选的，步骤A)中，加热溶解的温度为90～95℃，时间为2～3h；Preferably, in step A), the temperature of heating and dissolving is 90-95°C, and the time is 2-3h;
所述加热溶解在搅拌中进行，所述搅拌的转速为100～150r/min。The heating and dissolving are carried out in stirring, and the stirring speed is 100-150 r/min.
优选的，步骤B)中，将所述聚乙烯醇溶液、高岭土、分散剂和甲酰胺进行改性反应前，还包括：Preferably, in step B), before carrying out the modification reaction of the polyvinyl alcohol solution, kaolin, dispersant and formamide, it also includes:
将所述聚乙烯醇溶液降温至75～80℃；cooling the polyvinyl alcohol solution to 75-80°C;
所述改性反应的温度为75～80℃，时间为1～2h。The temperature of the modification reaction is 75-80° C., and the time is 1-2 h.
优选的，步骤C)中，将步骤B)改性反应后的产物、交联剂和消泡剂进行交联反应前，还包括：Preferably, in step C), before carrying out the cross-linking reaction of the product after the modification reaction in step B), the cross-linking agent and the defoaming agent, it also includes:
将步骤B)改性反应后的产物降温至50～60℃；Cool the product after the modification reaction in step B) to 50-60°C;
所述交联反应的温度为50～60℃，时间为1～2h；The temperature of the cross-linking reaction is 50-60° C., and the time is 1-2 h;
所述交联反应在搅拌的条件下进行，所述搅拌的转速为50～100r/min。The cross-linking reaction is carried out under stirring, and the stirring speed is 50-100 r/min.
本发明还提供了一种含有保护涂层的镀氧化铝薄膜，包括：The present invention also provides an aluminum oxide coating film containing a protective coating, comprising:
氧化铝基材膜；Alumina substrate film;
复合在所述氧化铝基材膜表面的保护涂层；a protective coating compounded on the surface of the alumina substrate film;
所述保护涂层由上文所述的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液形成，或所述保护涂层由上文所述的制备方法制得的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液形成。The protective coating is formed from the above-mentioned special polyvinyl alcohol emulsion for the aluminum-plated film protective coating, or the protective coating is special for the aluminum-plated thin-film protective coating prepared by the above-mentioned preparation method. A polyvinyl alcohol emulsion is formed.
本发明提供了一种镀氧化铝薄膜保护涂层专用聚乙烯醇乳液，由包括以下组分的原料制备得到：聚乙烯醇8wt％～15wt％；软水78wt％～87wt％；高岭土3wt％～5wt％；分散剂0.1wt％～0.5wt％；甲酰胺1wt％～3wt％；交联剂1wt％～3wt％；消泡剂0.05wt％～0.1wt％；以上各组分的用量之和为100％。本发明中，聚乙烯醇在软水中溶解后，添加高岭土、甲酰胺和分散剂，高岭土在分散剂的作用下，分散在聚乙烯醇乳液中，通过自身的基团在甲酰胺的作用下，屏蔽聚乙烯醇分子中的羟基，减少其与水进行亲和作用。在交联剂作用下，使聚乙烯醇线型分子相互连在一起，形成网状结构，提高涂层与基材膜的附着力。乳液反应完全后，通过加入适量的消泡剂即可消除产生的泡沫，同时又可以调节乳液体系的表面张力，便于更好的涂布应用。乳液涂在氧化铝基材膜上烘干后，高岭土分子以微观片状结构析出在涂层表面，有效提高了氧化铝基材膜耐龟裂、耐损伤性能，同时也避免了热水对聚乙烯醇涂层的破坏，确保高温蒸煮杀菌(121℃，45min)后薄膜外观保持透明的性能。因此，将本发明聚乙烯醇 乳液用于镀氧化铝薄膜保护涂层，镀氧化铝薄膜保护涂层专用聚乙烯醇乳液中的各组分协同作用，最终得到的镀氧化铝薄膜的综合性能较优。The invention provides a special polyvinyl alcohol emulsion for a protective coating of an aluminum oxide plated film, which is prepared from raw materials comprising the following components: polyvinyl alcohol 8wt%-15wt%; soft water 78wt%-87wt%; kaolin 3wt%-5wt% %; dispersant 0.1wt%～0.5wt%; formamide 1wt%～3wt%; crosslinking agent 1wt%～3wt%; defoamer 0.05wt%～0.1wt%; the sum of the above components is 100 %. In the present invention, after the polyvinyl alcohol is dissolved in soft water, kaolin, formamide and a dispersant are added, and the kaolin is dispersed in the polyvinyl alcohol emulsion under the action of the dispersant, and under the action of the formamide through its own group, Shield the hydroxyl group in the polyvinyl alcohol molecule and reduce its affinity with water. Under the action of the cross-linking agent, the linear molecules of polyvinyl alcohol are connected to each other to form a network structure, which improves the adhesion between the coating and the substrate film. After the emulsion reaction is complete, the foam can be eliminated by adding an appropriate amount of defoaming agent, and at the same time, the surface tension of the emulsion system can be adjusted to facilitate better coating applications. After the emulsion is coated on the alumina substrate film and dried, the kaolin molecules are precipitated on the surface of the coating in a micro-flaky structure, which effectively improves the crack resistance and damage resistance of the aluminum oxide substrate film, and also avoids hot water to polymerize. The destruction of the vinyl alcohol coating ensures that the appearance of the film remains transparent after high-temperature retort sterilization (121°C, 45min). Therefore, the polyvinyl alcohol emulsion of the present invention is used for the protective coating of the aluminum oxide film, and the various components in the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film work synergistically, and the overall performance of the finally obtained aluminum oxide film is better than that of the aluminum oxide film. excellent.
采用本发明的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液制备保护涂层，克服了常规聚乙烯醇做镀氧化铝保护涂层在湿热杀菌后外观发白的缺陷，拓宽了镀氧化铝薄膜在包装领域的应用。The protective coating is prepared by using the special polyvinyl alcohol emulsion for the protective coating of the alumina-plated film of the present invention, which overcomes the defect that the conventional polyvinyl alcohol is used as the alumina-plated protective coating and has a whitish appearance after moist heat sterilization, and broadens the scope of the alumina-plated film. Application in the field of packaging.
具体实施方式Detailed ways
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
本发明提供了一种镀氧化铝薄膜保护涂层专用聚乙烯醇乳液，由包括以下组分的原料制备得到：The invention provides a special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film, which is prepared from the raw materials comprising the following components:
Figure PCTCN2021110174-appb-000002
Figure PCTCN2021110174-appb-000002
以上各组分的用量之和为100％。The sum of the amounts of the above components is 100%.
本发明提供的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液由包括上文所述组分的原料经过溶解乳化制备得到。The special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention is prepared by dissolving and emulsification of the raw materials including the above-mentioned components.
本发明提供的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液的制备原料包括聚乙烯醇。在本发明的某些实施例中，所述聚乙烯醇在制备原料中的含量为8wt％、15wt％、10wt％、9wt％或13wt％。The preparation raw materials of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention include polyvinyl alcohol. In some embodiments of the present invention, the content of the polyvinyl alcohol in the preparation raw material is 8 wt %, 15 wt %, 10 wt %, 9 wt % or 13 wt %.
在本发明的某些实施例中，所述聚乙烯醇的聚合度为400～1900，醇解度为88％～99％。In some embodiments of the present invention, the degree of polymerization of the polyvinyl alcohol is 400-1900, and the degree of alcoholysis is 88%-99%.
本发明提供的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液的制备原料还包 括软水。在本发明的某些实施例中，所述软水在制备原料中的含量为82wt％、78wt％、81wt％或80wt％。The preparation raw materials of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also include soft water. In some embodiments of the present invention, the content of the soft water in the preparation raw material is 82 wt %, 78 wt %, 81 wt % or 80 wt %.
本发明对所述软水的来源并无特殊的限制，在本发明的某些实施例中，所述软水可以通过树脂交换制备得到。本发明对所述树脂交换的方法并无特殊的限制，采用本领域技术人员熟知的树脂交换的方法即可。The present invention has no special limitation on the source of the soft water. In some embodiments of the present invention, the soft water can be prepared by resin exchange. The method of the resin exchange is not particularly limited in the present invention, and the resin exchange method well known to those skilled in the art can be used.
本发明提供的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液的制备原料还包括高岭土。在本发明的某些实施例中，所述高岭土在制备原料中的含量为4wt％、3wt％、4.5wt％、5wt％或3.4wt％。The raw material for preparing the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also includes kaolin. In certain embodiments of the present invention, the content of the kaolin clay in the preparation raw material is 4 wt %, 3 wt %, 4.5 wt %, 5 wt % or 3.4 wt %.
在本发明的某些实施例中，所述高岭土的粒径为20～100nm。In some embodiments of the present invention, the particle size of the kaolin is 20-100 nm.
本发明提供的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液的制备原料还包括分散剂。在本发明的某些实施例中，所述分散剂在制备原料中的含量为0.5wt％、0.25wt％、0.4wt％、0.32wt％或0.1wt％。The preparation raw material of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also includes a dispersant. In some embodiments of the present invention, the content of the dispersant in the preparation raw material is 0.5 wt %, 0.25 wt %, 0.4 wt %, 0.32 wt % or 0.1 wt %.
在本发明的某些实施例中，所述分散剂选自聚丙烯酸钠和/或六偏磷酸钠。In certain embodiments of the present invention, the dispersing agent is selected from sodium polyacrylate and/or sodium hexametaphosphate.
本发明提供的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液的制备原料还包括甲酰胺。在本发明的某些实施例中，所述甲酰胺在制备原料中的含量为2.4wt％、2.7wt％、1.03wt％、3wt％或1wt％。The preparation raw material of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also includes formamide. In some embodiments of the present invention, the content of the formamide in the preparation raw material is 2.4 wt %, 2.7 wt %, 1.03 wt %, 3 wt % or 1 wt %.
本发明提供的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液的制备原料还包括交联剂。在本发明的某些实施例中，所述交联剂在制备原料中的含量为3wt％、1wt％、2.6wt％或1.44wt％。The preparation raw material of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also includes a crosslinking agent. In some embodiments of the present invention, the content of the cross-linking agent in the preparation raw material is 3 wt %, 1 wt %, 2.6 wt % or 1.44 wt %.
在本发明的某些实施例中，所述交联剂为二叔丁基过氧化物。In certain embodiments of the present invention, the crosslinking agent is di-tert-butyl peroxide.
本发明提供的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液的制备原料还包括消泡剂。在本发明的某些实施例中，所述消泡剂在制备原料中的含量为0.1wt％、0.05wt％、0.07wt％、0.08wt％或0.06wt％。The preparation raw materials of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film provided by the present invention also include a defoamer. In certain embodiments of the present invention, the content of the defoaming agent in the preparation raw material is 0.1 wt %, 0.05 wt %, 0.07 wt %, 0.08 wt % or 0.06 wt %.
在本发明的某些实施例中，所述消泡剂为乙醇和/或异丙醇。In certain embodiments of the present invention, the antifoaming agent is ethanol and/or isopropanol.
本发明还提供了一种上文所述的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液的制备方法，包括以下步骤：The present invention also provides a preparation method of the above-mentioned special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film, comprising the following steps:
A)将软水和聚乙烯醇加热溶解，得到聚乙烯醇溶液；A) heating and dissolving soft water and polyvinyl alcohol to obtain polyvinyl alcohol solution;
B)将所述聚乙烯醇溶液、高岭土、分散剂和甲酰胺进行改性反应；B) carrying out modification reaction with described polyvinyl alcohol solution, kaolin, dispersant and formamide;
C)将步骤B)改性反应后的产物、交联剂和消泡剂进行交联反应，得到 镀氧化铝薄膜保护涂层专用聚乙烯醇乳液。C) carry out cross-linking reaction with the product after step B) modification reaction, cross-linking agent and defoamer, obtain the special-purpose polyvinyl alcohol emulsion of aluminum oxide film protective coating.
所述镀氧化铝薄膜保护涂层专用聚乙烯醇乳液的制备方法中，采用的原料组分及配比同上，在此不再赘述。In the preparation method of the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide plated film, the raw material components and proportions used are the same as above, which will not be repeated here.
本发明先将软水和聚乙烯醇加热溶解，得到聚乙烯醇溶液。In the present invention, soft water and polyvinyl alcohol are heated and dissolved to obtain a polyvinyl alcohol solution.
在本发明的某些实施例中，所述加热溶解的温度为90～95℃，时间为2～3h。在某些实施例中，所述加热溶解的温度为95℃、93℃、90℃或91℃。在某些实施例中，所述加热溶解的时间为3h。在本发明的某些实施例中，所述加热溶解在搅拌中进行，所述搅拌的转速为100～150r/min。在某些实施例中，所述搅拌的转速为150r/min、140r/min、130r/min或100r/min。In some embodiments of the present invention, the temperature of the heating and dissolving is 90-95° C., and the time is 2-3 hours. In certain embodiments, the temperature for heating and dissolving is 95°C, 93°C, 90°C or 91°C. In some embodiments, the heating and dissolving time is 3h. In some embodiments of the present invention, the heating and dissolving are performed in stirring, and the stirring speed is 100-150 r/min. In certain embodiments, the rotational speed of the stirring is 150 r/min, 140 r/min, 130 r/min or 100 r/min.
得到聚乙烯醇溶液后，将所述聚乙烯醇溶液、高岭土、分散剂和甲酰胺进行改性反应。After the polyvinyl alcohol solution is obtained, the polyvinyl alcohol solution, kaolin, dispersant and formamide are subjected to a modification reaction.
在本发明的某些实施例中，将所述聚乙烯醇溶液、高岭土、分散剂和甲酰胺进行改性反应前，还包括：In some embodiments of the present invention, before carrying out the modification reaction of the polyvinyl alcohol solution, kaolin, dispersant and formamide, it also includes:
将所述聚乙烯醇溶液降温至75～80℃。The polyvinyl alcohol solution was cooled to 75-80°C.
本发明中，将所述聚乙烯醇溶液降温后的温度积为改性反应的温度。In the present invention, the temperature product of cooling the polyvinyl alcohol solution is the temperature of the modification reaction.
在本发明的某些实施例中，所述改性反应的温度为75～80℃，时间为1～2h。在某些实施例中，所述改性反应的温度为80℃、75℃、79℃或78℃。在某些实施例中，所述改性反应的时间为1h。In some embodiments of the present invention, the temperature of the modification reaction is 75-80° C., and the time is 1-2 h. In certain embodiments, the temperature of the modification reaction is 80°C, 75°C, 79°C, or 78°C. In certain embodiments, the modification reaction time is 1 h.
改性反应完成后，将所述改性反应后的产物、交联剂和消泡剂进行交联反应，得到镀氧化铝薄膜保护涂层专用聚乙烯醇乳液。After the modification reaction is completed, the product after the modification reaction, the crosslinking agent and the defoaming agent are subjected to a crosslinking reaction to obtain a special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film.
在本发明的某些实施例中，将所述改性反应后的产物、交联剂和消泡剂进行交联反应前，还包括：In some embodiments of the present invention, before the product after the modification reaction, the cross-linking agent and the defoaming agent are subjected to the cross-linking reaction, it also includes:
将所述改性反应后的产物降温至50～60℃。The product after the modification reaction is cooled to 50-60°C.
本发明中，将所述改性反应后的产物降温后的温度为交联反应的温度。In the present invention, the temperature after cooling the product after the modification reaction is the temperature of the crosslinking reaction.
在本发明的某些实施例中，所述交联反应的温度为50～60℃，时间为1～2h。在某些实施例中，所述交联反应的温度为60℃、50℃、55℃或58℃。在某些实施例中，所述交联反应的时间为1h、1.5h、2h、1.4h或1.6h。在本发明的某些实施例中，所述交联反应在搅拌的条件下进行，所述搅拌的转速为50～100r/min。在某些实施例中，所述搅拌的转速为50r/min、80r/min、70r/min、100 r/min或90r/min。In some embodiments of the present invention, the temperature of the cross-linking reaction is 50-60° C., and the time is 1-2 h. In certain embodiments, the temperature of the crosslinking reaction is 60°C, 50°C, 55°C, or 58°C. In certain embodiments, the time of the crosslinking reaction is 1 h, 1.5 h, 2 h, 1.4 h or 1.6 h. In some embodiments of the present invention, the cross-linking reaction is carried out under stirring, and the stirring speed is 50-100 r/min. In certain embodiments, the rotational speed of the stirring is 50 r/min, 80 r/min, 70 r/min, 100 r/min or 90 r/min.
在本发明的某些实施例中，将所述改性反应后的产物、交联剂和消泡剂进行交联反应后，还包括静置和冷却。在本发明的某些实施例中，冷却至室温。In some embodiments of the present invention, after the product after the modification reaction, the crosslinking agent and the defoaming agent are subjected to the crosslinking reaction, the method further includes standing and cooling. In certain embodiments of the invention, cooling to room temperature.
本发明还提供了一种含有保护涂层的镀氧化铝薄膜，包括：The present invention also provides an aluminum oxide coating film containing a protective coating, comprising:
氧化铝基材膜；Alumina substrate film;
复合在所述氧化铝基材膜表面的保护涂层；a protective coating compounded on the surface of the alumina substrate film;
所述保护涂层由上文所述的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液形成，或所述保护涂层由上文所述的制备方法制得的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液形成。The protective coating is formed from the above-mentioned special polyvinyl alcohol emulsion for the aluminum-plated film protective coating, or the protective coating is special for the aluminum-plated thin-film protective coating prepared by the above-mentioned preparation method. A polyvinyl alcohol emulsion is formed.
本发明对所述氧化铝基材膜的种类和来源并无特殊的限制，在本发明的某些实施例中，所述氧化铝基材膜可以按照中国专利CN108570644A记载的制备方法制备得到。The present invention has no special limitation on the type and source of the alumina substrate film. In some embodiments of the present invention, the alumina substrate film can be prepared according to the preparation method described in Chinese Patent CN108570644A.
在本发明的某些实施例中，所述氧化铝基材膜按照以下方法进行制备：In certain embodiments of the present invention, the alumina substrate film is prepared according to the following method:
在真空度达到5×10 -4MPa以上时，将铝丝在1600～1800℃熔化、蒸发，与此同时通入纯度为95％～99％的高纯氧，从而在基材膜的表面形成氧化铝层，得到氧化铝基材膜。 When the vacuum degree reaches 5×10 -4 MPa or more, the aluminum wire is melted and evaporated at 1600-1800 ℃, and at the same time, high-purity oxygen with a purity of 95%-99% is introduced to form the surface of the substrate film. Alumina layer was obtained to obtain an alumina base film.
在本发明的某些实施例中，所述氧化铝基材膜的制备在真空室中进行。在本发明的某些实施例中，铝丝的熔化和蒸发在蒸发舟中进行。高纯氧的通入可以使得铝蒸汽和氧气发生反应生成氧化铝，沉积至基材膜的表面，经过冷却后，即可得到氧化铝基材膜。在本发明的某些实施例中，基材膜的材质可以选自PET。在本发明的某些实施例中，基材膜的厚度为12～14μm。在某些实施例中，基材膜的厚度为12μm PET、13μm PET或14μm PET。在本发明的某些实施例中，所述氧化铝层的厚度为0.01～0.03μm。在某些实施例中，所述氧化铝层的厚度为0.01μm、0.03μm或0.02μm。In certain embodiments of the present invention, the preparation of the alumina substrate film is performed in a vacuum chamber. In certain embodiments of the present invention, the melting and evaporation of the aluminum wire is performed in an evaporation boat. The introduction of high-purity oxygen can make aluminum vapor react with oxygen to form aluminum oxide, which is deposited on the surface of the substrate film, and after cooling, the aluminum oxide substrate film can be obtained. In some embodiments of the present invention, the material of the substrate film can be selected from PET. In certain embodiments of the present invention, the thickness of the substrate film is 12-14 μm. In certain embodiments, the thickness of the substrate film is 12 μm PET, 13 μm PET, or 14 μm PET. In some embodiments of the present invention, the aluminum oxide layer has a thickness of 0.01-0.03 μm. In certain embodiments, the aluminum oxide layer has a thickness of 0.01 μm, 0.03 μm, or 0.02 μm.
在本发明的某些实施例中，所述保护涂层的厚度为0.3～0.5μm。在某些实施例中，所述保护涂层的厚度为0.3μm、0.5um、0.4um、0.45um或0.35μm。In some embodiments of the present invention, the thickness of the protective coating is 0.3-0.5 μm. In certain embodiments, the protective coating has a thickness of 0.3 μm, 0.5 μm, 0.4 μm, 0.45 μm, or 0.35 μm.
在本发明的某些实施例中，含有保护涂层的镀氧化铝薄膜按照以下方法进行制备：In certain embodiments of the present invention, the aluminum oxide-coated film containing the protective coating is prepared according to the following method:
在氧化铝基材膜表面采用逆转吻式涂布方式涂布保护乳液，烘干后，在氧 化铝基材膜表面形成保护涂层，得到涂有保护涂层的镀氧化铝薄膜；A protective emulsion is applied on the surface of the aluminum oxide substrate film by a reverse kiss coating method, and after drying, a protective coating is formed on the surface of the aluminum oxide substrate film to obtain an aluminum oxide plated film coated with the protective coating;
所述保护乳液为上文所述的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液，或上文所述的制备方法制得的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液。The protective emulsion is the above-mentioned special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film, or the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film prepared by the above-mentioned preparation method.
在本发明的某些实施例中，所述涂布的涂布辊参数为120～150目。在某些实施例中，所述涂布的涂布辊参数为120目、130目、140目、150目或145目。In some embodiments of the present invention, the parameters of the coating roll of the coating are 120-150 meshes. In certain embodiments, the coating roll parameters are 120 mesh, 130 mesh, 140 mesh, 150 mesh or 145 mesh.
在本发明的某些实施例中，所述烘干的温度为90～110℃。在某些实施例中，所述烘干的温度为90℃、100℃、110℃、105℃或95℃。在某些实施例中，所述烘干采用热风烘干。In some embodiments of the present invention, the drying temperature is 90-110°C. In certain embodiments, the drying temperature is 90°C, 100°C, 110°C, 105°C or 95°C. In some embodiments, the drying adopts hot air drying.
在本发明的某些实施例中，所述涂布的涂布量为0.3～0.5g/m 2。在某些实施例中，所述涂布的涂布量为0.3g/m 2、0.5g/m 2、0.4g/m 2、0.45g/m 2或0.35g/m 2。 In some embodiments of the present invention, the coating weight of the coating is 0.3-0.5 g/m 2 . In certain embodiments, the coating weight is 0.3 g/m 2 , 0.5 g/m 2 , 0.4 g/m 2 , 0.45 g/m 2 or 0.35 g/m 2 .
本发明对上文采用的原料的来源并无特殊的限制，可以为一般市售。The present invention has no special limitation on the source of the raw materials used above, and can be generally commercially available.
本发明中，聚乙烯醇在软水中溶解后，添加高岭土、甲酰胺和分散剂，高岭土在分散剂的作用下，分散在聚乙烯醇乳液中，通过自身的基团在甲酰胺的作用下，屏蔽聚乙烯醇分子中的羟基，减少其与水进行亲和作用。在交联剂作用下，使聚乙烯醇线型分子相互连在一起，形成网状结构，提高涂层与基材膜的附着力。乳液反应完全后，通过加入适量的消泡剂即可消除产生的泡沫，同时又可以调节乳液体系的表面张力，便于更好的涂布应用。乳液涂在氧化铝基材膜上烘干后，高岭土分子以微观片状结构析出在涂层表面，有效提高了氧化铝基材膜耐龟裂、耐损伤性能，同时也避免了热水对聚乙烯醇涂层的破坏，确保高温蒸煮杀菌(121℃，45min)后薄膜外观保持透明的性能。因此，将本发明聚乙烯醇乳液用于镀氧化铝薄膜保护涂层，镀氧化铝薄膜保护涂层专用聚乙烯醇乳液中的各组分协同作用，最终得到的镀氧化铝薄膜的综合性能较优。In the present invention, after the polyvinyl alcohol is dissolved in soft water, kaolin, formamide and a dispersant are added, and the kaolin is dispersed in the polyvinyl alcohol emulsion under the action of the dispersant, and under the action of the formamide through its own group, Shield the hydroxyl group in the polyvinyl alcohol molecule and reduce its affinity with water. Under the action of the cross-linking agent, the linear molecules of polyvinyl alcohol are connected to each other to form a network structure, which improves the adhesion between the coating and the substrate film. After the emulsion reaction is complete, the foam can be eliminated by adding an appropriate amount of defoaming agent, and at the same time, the surface tension of the emulsion system can be adjusted to facilitate better coating applications. After the emulsion is coated on the alumina substrate film and dried, the kaolin molecules are precipitated on the surface of the coating in a micro-flaky structure, which effectively improves the crack resistance and damage resistance of the aluminum oxide substrate film, and also avoids hot water to polymerize. The destruction of the vinyl alcohol coating ensures that the appearance of the film remains transparent after high-temperature retort sterilization (121°C, 45min). Therefore, the polyvinyl alcohol emulsion of the present invention is used for the protective coating of the aluminum oxide film, and the various components in the special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film work synergistically, and the overall performance of the finally obtained aluminum oxide film is better than that of the aluminum oxide film. excellent.
采用本发明的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液制备保护涂层，克服了常规聚乙烯醇做镀氧化铝保护涂层在湿热杀菌后外观发白的缺陷，拓宽了镀氧化铝薄膜在包装领域的应用。The protective coating is prepared by using the special polyvinyl alcohol emulsion for the protective coating of the alumina-plated film of the present invention, which overcomes the defect that the conventional polyvinyl alcohol is used as the alumina-plated protective coating and has a whitish appearance after moist heat sterilization, and broadens the scope of the alumina-plated film. Application in the field of packaging.
为了进一步说明本发明，以下结合实施例对本发明提供的一种镀氧化铝薄膜保护涂层专用聚乙烯醇乳液、其制备方法及应用进行详细描述，但不能将其理解为对本发明保护范围的限定。In order to further illustrate the present invention, a special polyvinyl alcohol emulsion for aluminum oxide film protective coating provided by the present invention, its preparation method and application will be described in detail below with reference to the examples, but it should not be construed as a limitation on the protection scope of the present invention .
以下实施例中所用的试剂均为市售。The reagents used in the following examples are all commercially available.
实施例中，按照标准GB/T 1038检测所述镀氧化铝薄膜的氧气透过率；按照标准GB/T 1037检测所述镀氧化铝薄膜的水蒸气透过率；按照标准BB/T 0003-1994检测所述镀氧化铝薄膜经过高温蒸煮(121℃，45min)杀菌后的外观。In the embodiment, the oxygen transmission rate of the aluminum oxide film is detected according to the standard GB/T 1038; the water vapor transmission rate of the aluminum oxide film is detected according to the standard GB/T 1037; according to the standard BB/T 0003- In 1994, the appearance of the alumina-plated film after being sterilized by high-temperature cooking (121°C, 45min) was tested.
实施例1Example 1
聚乙烯醇乳液的制备原料包括：The raw materials for the preparation of polyvinyl alcohol emulsion include:
Figure PCTCN2021110174-appb-000003
Figure PCTCN2021110174-appb-000003
所述聚乙烯醇的聚合度为400，醇解度为99％；The degree of polymerization of the polyvinyl alcohol is 400, and the degree of alcoholysis is 99%;
所述高岭土的粒径为20～100nm；The particle size of the kaolin is 20-100 nm;
所述分散剂为聚丙烯酸钠；The dispersant is sodium polyacrylate;
所述交联剂为二叔丁基过氧化物；The crosslinking agent is di-tert-butyl peroxide;
所述消泡剂为乙醇。The defoamer is ethanol.
制备方法包括：Preparation methods include:
在反应釜中加入软水和聚乙烯醇，开启搅拌，转速为150r/min，升温到95℃保持3h，使其完全溶解；然后降温至80℃，加入高岭土、分散剂和甲酰胺，保温1h，待改性反应完全后，通过冷却水降温到60℃，加入交联剂和消泡剂进行交联反应，并将搅拌速度降低至50r/min，充分搅拌1h后，静置，冷却至室温后出料，得到聚乙烯醇乳液。Add soft water and polyvinyl alcohol to the reaction kettle, turn on stirring, the speed is 150r/min, heat up to 95°C for 3h to make it completely dissolved; then cool down to 80°C, add kaolin, dispersant and formamide, keep for 1h, After the modification reaction is completed, cool it down to 60 ℃ by cooling water, add a crosslinking agent and a defoaming agent to carry out the crosslinking reaction, reduce the stirring speed to 50r/min, fully stir for 1 hour, let it stand, and cool to room temperature. The material is discharged to obtain a polyvinyl alcohol emulsion.
将厚度为12μm的卷筒PET基材薄膜置于真空室内，关闭真空室抽真空，当真空度达到5×10 -4MPa以上时，将蒸发舟升温至1600℃，然后再把纯度为95％的铝丝连续送至蒸发舟上，使铝丝在蒸发舟上连续地熔化、蒸发，同时通入纯度为95％的高纯氧，铝蒸汽和氧气发生反应生成氧化铝，从而移动到薄膜 表面经冷却后，在基材膜的表面形成0.01μm的氧化铝层，得到氧化铝基材膜。 Place the 12μm-thick roll PET substrate film in a vacuum chamber, close the vacuum chamber and evacuate. When the vacuum degree reaches 5×10 -4 MPa or more, the evaporation boat is heated to 1600°C, and then the purity is 95%. The aluminum wire is continuously sent to the evaporation boat, so that the aluminum wire is continuously melted and evaporated on the evaporation boat, and at the same time, high-purity oxygen with a purity of 95% is introduced, and the aluminum vapor reacts with the oxygen to form alumina, which moves to the surface of the film After cooling, an alumina layer of 0.01 μm was formed on the surface of the base film to obtain an alumina base film.
在氧化铝基材膜表面通过逆转吻式涂布方式涂布所述聚乙烯醇乳液，涂布辊参数为120目，涂层涂布量为0.3g/m 2，厚度为0.3μm，烘箱温度为90℃，经热风烘干后，在氧化铝基材膜表面形成保护涂层，得到含有保护涂层的镀氧化铝薄膜。 The polyvinyl alcohol emulsion was coated on the surface of the alumina substrate film by reverse kiss coating, the parameters of the coating roller were 120 mesh, the coating weight was 0.3 g/m 2 , the thickness was 0.3 μm, and the oven temperature was The temperature is 90° C., and after being dried by hot air, a protective coating is formed on the surface of the alumina substrate film to obtain an alumina-plated film containing the protective coating.
对含有保护涂层的镀氧化铝薄膜的氧气透过率、水蒸气透过率及高温蒸煮(121℃，45min)杀菌后外观进行检测，实验结果表明，含有保护涂层的镀氧化铝薄膜的氧气透过率为0.6cc/m 2·day，水蒸气透过率为0.9g/m 2·day，经过高温蒸煮(121℃，45min)杀菌后外观透明。 The oxygen transmission rate, water vapor transmission rate and high temperature cooking (121℃, 45min) after sterilization of the aluminum oxide film with protective coating were tested. The experimental results show that the aluminum oxide film with protective coating The oxygen transmission rate is 0.6cc/m 2 ·day, the water vapor transmission rate is 0.9g/m 2 ·day, and the appearance is transparent after being sterilized by high temperature cooking (121℃, 45min).
实施例2Example 2
聚乙烯醇乳液的制备原料包括：The raw materials for the preparation of polyvinyl alcohol emulsion include:
Figure PCTCN2021110174-appb-000004
Figure PCTCN2021110174-appb-000004
所述聚乙烯醇的聚合度为1900，醇解度为88％；The degree of polymerization of the polyvinyl alcohol is 1900, and the degree of alcoholysis is 88%;
所述高岭土的粒径为20～100nm；The particle size of the kaolin is 20-100 nm;
所述分散剂为六偏磷酸钠；Described dispersant is sodium hexametaphosphate;
所述交联剂为二叔丁基过氧化物；The crosslinking agent is di-tert-butyl peroxide;
所述消泡剂为异丙醇。The defoamer is isopropanol.
制备方法包括：Preparation methods include:
在反应釜中加入软水和聚乙烯醇，开启搅拌，转速为140r/min，升温到93℃保持3h，使其完全溶解；然后降温至75℃，加入高岭土、分散剂和甲酰胺，保温1h，待改性反应完全后，通过冷却水降温到50℃，加入交联剂和消泡剂进行交联反应，并将搅拌速度降低至80r/min，充分搅拌1.5h后，静置，冷却至室温后出料，得到聚乙烯醇乳液。Add soft water and polyvinyl alcohol to the reaction kettle, turn on stirring, the speed is 140r/min, heat up to 93°C for 3h to make it completely dissolved; then cool down to 75°C, add kaolin, dispersant and formamide, keep for 1h, After the modification reaction is completed, cool down to 50 ℃ by cooling water, add crosslinking agent and defoamer to carry out crosslinking reaction, reduce the stirring speed to 80r/min, fully stir for 1.5h, let stand and cool to room temperature After discharging, the polyvinyl alcohol emulsion is obtained.
将厚度为13μm的卷筒PET基材薄膜置于真空室内，关闭真空室抽真空，当真空度达到5×10 -4MPa以上时，将蒸发舟升温至1650℃，然后再把纯度为96％的铝丝连续送至蒸发舟上，使铝丝在蒸发舟上连续地熔化、蒸发，同时通入纯度为96％的高纯氧，铝蒸汽和氧气发生反应生成氧化铝，从而移动到薄膜表面经冷却后，在基材膜的表面形成0.03μm的氧化铝层，得到氧化铝基材膜。 Place the 13μm-thick roll PET substrate film in a vacuum chamber, close the vacuum chamber and evacuate. When the vacuum degree reaches 5×10 -4 MPa or more, the evaporation boat is heated to 1650°C, and then the purity is 96%. The aluminum wire is continuously sent to the evaporation boat, so that the aluminum wire is continuously melted and evaporated on the evaporation boat, and at the same time, high-purity oxygen with a purity of 96% is introduced, and the aluminum vapor and oxygen react to form alumina, which moves to the surface of the film After cooling, an alumina layer of 0.03 μm was formed on the surface of the base film to obtain an alumina base film.
在氧化铝基材膜表面通过逆转吻式涂布方式涂布所述聚乙烯醇乳液，涂布辊参数为130目，涂层涂布量为0.5g/m 2，厚度为0.5μm，烘箱温度为100℃，经热风烘干后，在氧化铝基材膜表面形成保护涂层，得到含有保护涂层的镀氧化铝薄膜。 The polyvinyl alcohol emulsion was coated on the surface of the alumina substrate film by reverse kiss coating, the coating roll parameter was 130 mesh, the coating weight was 0.5 g/m 2 , the thickness was 0.5 μm, and the oven temperature was The temperature is 100° C., and after being dried by hot air, a protective coating is formed on the surface of the alumina substrate film to obtain an alumina-plated film containing the protective coating.
对含有保护涂层的镀氧化铝薄膜的氧气透过率、水蒸气透过率及高温蒸煮(121℃，45min)杀菌后外观进行检测，实验结果表明，含有保护涂层的镀氧化铝薄膜的氧气透过率为1.0cc/m 2·day，水蒸气透过率为0.8g/m 2·day，经过高温蒸煮(121℃，45min)杀菌后外观透明。 The oxygen transmission rate, water vapor transmission rate and high temperature cooking (121℃, 45min) after sterilization of the aluminum oxide film with protective coating were tested. The experimental results show that the aluminum oxide film with protective coating The oxygen transmission rate is 1.0cc/m 2 ·day, the water vapor transmission rate is 0.8g/m 2 ·day, and the appearance is transparent after being sterilized by high temperature cooking (121℃, 45min).
实施例3Example 3
聚乙烯醇乳液的制备原料包括：The raw materials for the preparation of polyvinyl alcohol emulsion include:
Figure PCTCN2021110174-appb-000005
Figure PCTCN2021110174-appb-000005
所述聚乙烯醇的聚合度为500，醇解度为90％；The degree of polymerization of the polyvinyl alcohol is 500, and the degree of alcoholysis is 90%;
所述高岭土的粒径为20～100nm；The particle size of the kaolin is 20-100 nm;
所述分散剂为聚丙烯酸钠；The dispersant is sodium polyacrylate;
所述交联剂为二叔丁基过氧化物；The crosslinking agent is di-tert-butyl peroxide;
所述消泡剂为乙醇。The defoamer is ethanol.
制备方法包括：Preparation methods include:
在反应釜中加入软水和聚乙烯醇，开启搅拌，转速为130r/min，升温到 90℃保持3h，使其完全溶解；然后降温至79℃，加入高岭土、分散剂和甲酰胺，保温1h，待改性反应完全后，通过冷却水降温到55℃，加入交联剂和消泡剂进行交联反应，并将搅拌速度降低至70r/min，充分搅拌2h后，静置，冷却至室温后出料，得到聚乙烯醇乳液。Add soft water and polyvinyl alcohol to the reaction kettle, turn on stirring, the rotating speed is 130r/min, heat up to 90℃ for 3h to make it completely dissolved; then cool down to 79℃, add kaolin, dispersant and formamide, keep for 1h, After the modification reaction is complete, cool down to 55 ℃ by cooling water, add crosslinking agent and defoamer to carry out crosslinking reaction, reduce the stirring speed to 70r/min, fully stir for 2h, let stand, and cool to room temperature The material is discharged to obtain a polyvinyl alcohol emulsion.
将厚度为14μm的卷筒PET基材薄膜置于真空室内，关闭真空室抽真空，当真空度达到5×10 -4MPa以上时，将蒸发舟升温至1700℃，然后再把纯度为97％的铝丝连续送至蒸发舟上，使铝丝在蒸发舟上连续地熔化、蒸发，同时通入纯度为97％的高纯氧，铝蒸汽和氧气发生反应生成氧化铝，从而移动到薄膜表面经冷却后，在基材膜的表面形成0.02μm的氧化铝层，得到氧化铝基材膜。 Place the 14μm-thick roll PET substrate film in a vacuum chamber, close the vacuum chamber and evacuate, when the vacuum degree reaches 5×10 -4 MPa or more, the evaporation boat is heated to 1700°C, and then the purity is 97%. The aluminum wire is continuously sent to the evaporation boat, so that the aluminum wire is continuously melted and evaporated on the evaporation boat, and at the same time, high-purity oxygen with a purity of 97% is introduced, and the aluminum vapor and oxygen react to form alumina, which moves to the surface of the film After cooling, an alumina layer of 0.02 μm was formed on the surface of the base film to obtain an alumina base film.
在氧化铝基材膜表面通过逆转吻式涂布方式涂布所述聚乙烯醇乳液，涂布辊参数为140目，涂层涂布量为0.4g/m 2，厚度为0.4μm，烘箱温度为110℃，经热风烘干后，在氧化铝基材膜表面形成保护涂层，得到含有保护涂层的镀氧化铝薄膜。 The polyvinyl alcohol emulsion was coated on the surface of the alumina substrate film by reverse kiss coating, the coating roll parameter was 140 mesh, the coating weight was 0.4 g/m 2 , the thickness was 0.4 μm, and the oven temperature was The temperature is 110° C., and after drying with hot air, a protective coating is formed on the surface of the aluminum oxide base film to obtain an aluminum oxide plated film containing the protective coating.
对含有保护涂层的镀氧化铝薄膜的氧气透过率、水蒸气透过率及高温蒸煮(121℃，45min)杀菌后外观进行检测，实验结果表明，含有保护涂层的镀氧化铝薄膜的氧气透过率为0.7cc/m 2·day，水蒸气透过率为1.0g/m 2·day，经过高温蒸煮(121℃，45min)杀菌后外观透明。 The oxygen transmission rate, water vapor transmission rate and high temperature cooking (121℃, 45min) after sterilization of the aluminum oxide film with protective coating were tested. The experimental results show that the aluminum oxide film with protective coating The oxygen transmission rate is 0.7cc/m 2 ·day, the water vapor transmission rate is 1.0g/m 2 ·day, and the appearance is transparent after being sterilized by high temperature cooking (121℃, 45min).
实施例4Example 4
聚乙烯醇乳液的制备原料包括：The raw materials for the preparation of polyvinyl alcohol emulsion include:
Figure PCTCN2021110174-appb-000006
Figure PCTCN2021110174-appb-000006
所述聚乙烯醇的聚合度为1700，醇解度为95％；The degree of polymerization of the polyvinyl alcohol is 1700, and the degree of alcoholysis is 95%;
所述高岭土的粒径为20～100nm；The particle size of the kaolin is 20-100 nm;
所述分散剂为六偏磷酸钠；Described dispersant is sodium hexametaphosphate;
所述交联剂为二叔丁基过氧化物；The crosslinking agent is di-tert-butyl peroxide;
所述消泡剂为异丙醇。The defoamer is isopropanol.
制备方法包括：Preparation methods include:
在反应釜中加入软水和聚乙烯醇，开启搅拌，转速为100r/min，升温到91℃保持3h，使其完全溶解；然后降温至78℃，加入高岭土、分散剂和甲酰胺，保温1h，待改性反应完全后，通过冷却水降温到58℃，加入交联剂和消泡剂进行交联反应，并将搅拌速度降低至100r/min，充分搅拌1.4h后，静置，冷却至室温后出料，得到聚乙烯醇乳液。Add soft water and polyvinyl alcohol to the reaction kettle, turn on stirring, the rotation speed is 100r/min, heat up to 91 °C for 3 h to make it completely dissolved; then cool down to 78 °C, add kaolin, dispersant and formamide, keep for 1 h, After the modification reaction is completed, cool down to 58 ℃ by cooling water, add crosslinking agent and defoamer to carry out crosslinking reaction, reduce the stirring speed to 100r/min, fully stir for 1.4h, let stand, and cool to room temperature After discharging, a polyvinyl alcohol emulsion is obtained.
将厚度为13μm的卷筒PET基材薄膜置于真空室内，关闭真空室抽真空，当真空度达到5×10 -4MPa以上时，将蒸发舟升温至1750℃，然后再把纯度为98％的铝丝连续送至蒸发舟上，使铝丝在蒸发舟上连续地熔化、蒸发，同时通入纯度为98％的高纯氧，铝蒸汽和氧气发生反应生成氧化铝，从而移动到薄膜表面经冷却后，在基材膜的表面形成0.03μm的氧化铝层，得到氧化铝基材膜。 Place the 13μm-thick roll PET substrate film in a vacuum chamber, close the vacuum chamber and evacuate, when the vacuum degree reaches 5×10 -4 MPa or more, the evaporation boat is heated to 1750°C, and then the purity is 98%. The aluminum wire is continuously sent to the evaporation boat, so that the aluminum wire is continuously melted and evaporated on the evaporation boat, and at the same time, high-purity oxygen with a purity of 98% is introduced, and the aluminum vapor and oxygen react to form alumina, which moves to the surface of the film After cooling, an alumina layer of 0.03 μm was formed on the surface of the base film to obtain an alumina base film.
在氧化铝基材膜表面通过逆转吻式涂布方式涂布所述聚乙烯醇乳液，涂布辊参数为150目，涂层涂布量为0.45g/m 2，厚度为0.45μm，烘箱温度为105℃，经热风烘干后，在氧化铝基材膜表面形成保护涂层，得到含有保护涂层的镀氧化铝薄膜。 The polyvinyl alcohol emulsion was coated on the surface of the alumina substrate film by reverse kiss coating. The parameters of the coating roller were 150 mesh, the coating weight was 0.45 g/m 2 , the thickness was 0.45 μm, and the oven temperature was 0.45 μm. The temperature is 105° C., and after being dried by hot air, a protective coating is formed on the surface of the alumina substrate film to obtain an alumina-plated film containing the protective coating.
对含有保护涂层的镀氧化铝薄膜的氧气透过率、水蒸气透过率及高温蒸煮(121℃，45min)杀菌后外观进行检测，实验结果表明，含有保护涂层的镀氧化铝薄膜的氧气透过率为0.6cc/m 2·day，水蒸气透过率为0.5g/m 2·day，经过高温蒸煮(121℃，45min)杀菌后外观透明。 The oxygen transmission rate, water vapor transmission rate and high temperature cooking (121℃, 45min) after sterilization of the aluminum oxide film with protective coating were tested. The experimental results show that the aluminum oxide film with protective coating The oxygen transmission rate is 0.6cc/m 2 ·day, the water vapor transmission rate is 0.5g/m 2 ·day, and the appearance is transparent after being sterilized by high temperature cooking (121℃, 45min).
实施例5Example 5
聚乙烯醇乳液的制备原料包括：The raw materials for the preparation of polyvinyl alcohol emulsion include:
Figure PCTCN2021110174-appb-000007
Figure PCTCN2021110174-appb-000007
Figure PCTCN2021110174-appb-000008
Figure PCTCN2021110174-appb-000008
所述聚乙烯醇的聚合度为1500，醇解度为93％；The degree of polymerization of the polyvinyl alcohol is 1500, and the degree of alcoholysis is 93%;
所述高岭土的粒径为20～100nm；The particle size of the kaolin is 20-100 nm;
所述分散剂为聚丙烯酸钠；The dispersant is sodium polyacrylate;
所述交联剂为二叔丁基过氧化物；The crosslinking agent is di-tert-butyl peroxide;
所述消泡剂为乙醇。The defoamer is ethanol.
制备方法包括：Preparation methods include:
在反应釜中加入软水和聚乙烯醇，开启搅拌，转速为120r/min，升温到94℃保持3h，使其完全溶解；然后降温至77℃，加入高岭土、分散剂和甲酰胺，保温1h，待改性反应完全后，通过冷却水降温到53℃，加入交联剂和消泡剂进行交联反应，并将搅拌速度降低至90r/min，充分搅拌1.6h后，静置，冷却至室温后出料，得到聚乙烯醇乳液。Add soft water and polyvinyl alcohol to the reaction kettle, turn on stirring, the speed is 120r/min, heat up to 94°C for 3h to make it completely dissolved; then cool down to 77°C, add kaolin, dispersant and formamide, keep for 1h, After the modification reaction is completed, cool down to 53 ℃ by cooling water, add crosslinking agent and defoamer to carry out crosslinking reaction, reduce the stirring speed to 90r/min, fully stir for 1.6h, let stand, and cool to room temperature After discharging, the polyvinyl alcohol emulsion is obtained.
将厚度为12μm的卷筒PET基材薄膜置于真空室内，关闭真空室抽真空，当真空度达到5×10 -4MPa以上时，将蒸发舟升温至1800℃，然后再把纯度为99％的铝丝连续送至蒸发舟上，使铝丝在蒸发舟上连续地熔化、蒸发，同时通入纯度为99％的高纯氧，铝蒸汽和氧气发生反应生成氧化铝，从而移动到薄膜表面经冷却后，在基材膜的表面形成0.02μm的氧化铝层，得到氧化铝基材膜。 Place the 12μm-thick roll PET substrate film in a vacuum chamber, close the vacuum chamber and evacuate, when the vacuum degree reaches 5×10 -4 MPa or more, the evaporation boat is heated to 1800°C, and then the purity is 99%. The aluminum wire is continuously sent to the evaporation boat, so that the aluminum wire is continuously melted and evaporated on the evaporation boat, and high-purity oxygen with a purity of 99% is introduced at the same time. After cooling, an alumina layer of 0.02 μm was formed on the surface of the base film to obtain an alumina base film.
在氧化铝基材膜表面通过逆转吻式涂布方式涂布所述聚乙烯醇乳液，涂布辊参数为145目，涂层涂布量为0.35g/m 2，厚度为0.35μm，烘箱温度为95℃，经热风烘干后，在氧化铝基材膜表面形成保护涂层，得到含有保护涂层的镀氧化铝薄膜。 The polyvinyl alcohol emulsion was coated on the surface of the alumina substrate film by reverse kiss coating. The parameters of the coating roller were 145 mesh, the coating weight was 0.35 g/m 2 , the thickness was 0.35 μm, and the oven temperature was 0.35 μm. The temperature is 95° C., and after being dried by hot air, a protective coating is formed on the surface of the alumina substrate film to obtain an alumina-plated film containing the protective coating.
对含有保护涂层的镀氧化铝薄膜的氧气透过率、水蒸气透过率及高温蒸煮(121℃，45min)杀菌后外观进行检测，实验结果表明，含有保护涂层的镀氧化铝薄膜的氧气透过率为0.5cc/m 2·day，水蒸气透过率为0.8g/m 2·day，经过高温蒸煮(121℃，45min)杀菌后外观透明。 The oxygen transmission rate, water vapor transmission rate and high temperature cooking (121℃, 45min) after sterilization of the aluminum oxide film with protective coating were tested. The experimental results show that the aluminum oxide film with protective coating The oxygen transmission rate is 0.5cc/m 2 ·day, the water vapor transmission rate is 0.8g/m 2 ·day, and the appearance is transparent after being sterilized by high temperature cooking (121℃, 45min).
比较例1Comparative Example 1
将厚度为13μm的卷筒PET基材薄膜置于真空室内，关闭真空室抽真空，当真空度达到5×10 -4MPa以上时，将蒸发舟升温至1650℃，然后再把纯度为96％的铝丝连续送至蒸发舟上，使铝丝在蒸发舟上连续地熔化、蒸发，同时通 入纯度为96％的高纯氧，铝蒸汽和氧气发生反应生成氧化铝，从而移动到薄膜表面经冷却后，在基材膜的表面形成0.02μm的氧化铝层，得到氧化铝基材膜。 Place the 13μm-thick roll PET substrate film in a vacuum chamber, close the vacuum chamber and evacuate, when the vacuum degree reaches 5×10 -4 MPa or more, the evaporation boat is heated to 1650°C, and then the purity is 96%. The aluminum wire is continuously sent to the evaporation boat, so that the aluminum wire is continuously melted and evaporated on the evaporation boat. At the same time, high-purity oxygen with a purity of 96% is introduced, and the aluminum vapor and oxygen react to form alumina, which moves to the surface of the film After cooling, an alumina layer of 0.02 μm was formed on the surface of the base film to obtain an alumina base film.
在氧化铝基材膜表面通过逆转吻式涂布方式涂布CN102277049A中实施例1得到的乳液，涂布辊参数为130目，涂层涂布量为0.5g/m2，厚度为0.5μm，烘箱温度为100℃，经热风烘干后，在氧化铝基材膜表面形成保护涂层，得到含有保护涂层的镀氧化铝薄膜。The emulsion obtained in Example 1 of CN102277049A was coated on the surface of the alumina substrate film by reverse kiss coating, the coating roll parameter was 130 mesh, the coating weight was 0.5 g/m2, the thickness was 0.5 μm, and the oven The temperature is 100° C., and after being dried by hot air, a protective coating is formed on the surface of the aluminum oxide substrate film, and an aluminum oxide plated film containing the protective coating is obtained.
对含有保护涂层的镀氧化铝薄膜的氧气透过率、水蒸气透过率及高温蒸煮(121℃，45min)杀菌后外观进行检测，实验结果表明，含有保护涂层的镀氧化铝薄膜的氧气透过率为5cc/m 2·day，水蒸气透过率为8g/m 2·day，经过高温蒸煮(121℃，45min)杀菌后外观发白。 The oxygen transmission rate, water vapor transmission rate and high temperature cooking (121℃, 45min) after sterilization of the aluminum oxide film with protective coating were tested. The experimental results show that the aluminum oxide film with protective coating The oxygen transmission rate is 5cc/m 2 ·day, the water vapor transmission rate is 8g/m 2 ·day, and the appearance turns white after being sterilized by high temperature cooking (121℃, 45min).
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above description of the disclosed embodiments enables any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

  1. 一种镀氧化铝薄膜保护涂层专用聚乙烯醇乳液，由包括以下组分的原料经过溶解乳化制备得到：A special polyvinyl alcohol emulsion for a protective coating of an aluminum oxide film is prepared by dissolving and emulsification of raw materials comprising the following components:
    Figure PCTCN2021110174-appb-100001
    Figure PCTCN2021110174-appb-100001
    以上各组分的用量之和为100％。The sum of the amounts of the above components is 100%.
  2. 根据权利要求1所述的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液，其特征在于，所述聚乙烯醇的聚合度为400～1900，醇解度为88％～99％。The special polyvinyl alcohol emulsion for aluminum oxide film protective coating according to claim 1, wherein the polyvinyl alcohol has a polymerization degree of 400-1900 and an alcoholysis degree of 88%-99%.
  3. 根据权利要求1所述的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液，其特征在于，所述高岭土的粒径为20～100nm。The special polyvinyl alcohol emulsion for protective coating of aluminum oxide film according to claim 1, wherein the particle size of the kaolin is 20-100 nm.
  4. 根据权利要求1所述的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液，其特征在于，所述的分散剂选自聚丙烯酸钠和/或六偏磷酸钠；The special polyvinyl alcohol emulsion for aluminum oxide film protective coating according to claim 1, is characterized in that, described dispersant is selected from sodium polyacrylate and/or sodium hexametaphosphate;
    所述交联剂为二叔丁基过氧化物。The crosslinking agent is di-tert-butyl peroxide.
  5. 根据权利要求1所述的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液，其特征在于，所述消泡剂为乙醇和/或异丙醇。The special-purpose polyvinyl alcohol emulsion for aluminum oxide film protective coating according to claim 1, wherein the defoamer is ethanol and/or isopropanol.
  6. 权利要求1所述的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液的制备方法，包括以下步骤：The preparation method of the special-purpose polyvinyl alcohol emulsion of aluminum oxide film protective coating described in claim 1, comprises the following steps:
    A)将软水和聚乙烯醇加热溶解，得到聚乙烯醇溶液；A) heating and dissolving soft water and polyvinyl alcohol to obtain polyvinyl alcohol solution;
    B)将所述聚乙烯醇溶液、高岭土、分散剂和甲酰胺进行改性反应；B) carrying out modification reaction with described polyvinyl alcohol solution, kaolin, dispersant and formamide;
    C)将步骤B)改性反应后的产物、交联剂和消泡剂进行交联反应，得到镀氧化铝薄膜保护涂层专用聚乙烯醇乳液。C) subjecting the product after the modification reaction in step B), the crosslinking agent and the defoaming agent to a crosslinking reaction to obtain a special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film.
  7. 根据权利要求6所述的制备方法，其特征在于，步骤A)中，加热溶解的温度为90～95℃，时间为2～3h；The preparation method according to claim 6, wherein, in step A), the temperature of heating and dissolving is 90～95°C, and the time is 2～3h;
    所述加热溶解在搅拌中进行，所述搅拌的转速为100～150r/min。The heating and dissolving are carried out in stirring, and the stirring speed is 100-150 r/min.
  8. 根据权利要求6所述的制备方法，其特征在于，步骤B)中，将所述聚乙烯醇溶液、高岭土、分散剂和甲酰胺进行改性反应前，还包括：The preparation method according to claim 6, is characterized in that, in step B), before carrying out modification reaction with described polyvinyl alcohol solution, kaolin, dispersant and formamide, also comprises:
    将所述聚乙烯醇溶液降温至75～80℃；cooling the polyvinyl alcohol solution to 75-80°C;
    所述改性反应的温度为75～80℃，时间为1～2h。The temperature of the modification reaction is 75-80° C., and the time is 1-2 h.
  9. 根据权利要求1所述的制备方法，其特征在于，步骤C)中，将步骤B)改性反应后的产物、交联剂和消泡剂进行交联反应前，还包括：The preparation method according to claim 1, characterized in that, in step C), before the product, cross-linking agent and defoaming agent after the modification reaction in step B) are subjected to the cross-linking reaction, further comprising:
    将步骤B)改性反应后的产物降温至50～60℃；Cool the product after the modification reaction in step B) to 50-60°C;
    所述交联反应的温度为50～60℃，时间为1～2h；The temperature of the cross-linking reaction is 50-60° C., and the time is 1-2 h;
    所述交联反应在搅拌的条件下进行，所述搅拌的转速为50～100r/min。The cross-linking reaction is carried out under stirring, and the stirring speed is 50-100 r/min.
  10. 一种含有保护涂层的镀氧化铝薄膜，包括：An aluminum oxide-coated film with a protective coating comprising:
    氧化铝基材膜；Alumina substrate film;
    复合在所述氧化铝基材膜表面的保护涂层；a protective coating compounded on the surface of the alumina substrate film;
    所述保护涂层由权利要求1～5任意一项所述的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液形成，或所述保护涂层由权利要求6～9任意一项所述的制备方法制得的镀氧化铝薄膜保护涂层专用聚乙烯醇乳液形成。The protective coating is formed by the special polyvinyl alcohol emulsion described in any one of claims 1 to 5, or the protective coating is prepared by any one of claims 6 to 9. The special polyvinyl alcohol emulsion for the protective coating of the aluminum oxide film prepared by the method is formed.
PCT/CN2021/110174 2021-03-31 2021-08-03 Special polyvinyl alcohol emulsion for protective coating for aluminum oxide-coated film, and preparation method for and application of polyvinyl alcohol emulsion WO2022205720A1 (en)

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