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CN114933726A - High-barrier composite film and preparation method thereof - Google Patents

High-barrier composite film and preparation method thereof Download PDF

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Publication number
CN114933726A
CN114933726A CN202210470779.8A CN202210470779A CN114933726A CN 114933726 A CN114933726 A CN 114933726A CN 202210470779 A CN202210470779 A CN 202210470779A CN 114933726 A CN114933726 A CN 114933726A
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China
Prior art keywords
layer
barrier composite
bottom layer
composite film
middle layer
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Pending
Application number
CN202210470779.8A
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Chinese (zh)
Inventor
曾祥平
汪星星
吴明忠
刘华
郑梅良
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Zhejiang Changyu New Material Co ltd
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Zhejiang Changyu New Material Co ltd
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Priority to CN202210470779.8A priority Critical patent/CN114933726A/en
Publication of CN114933726A publication Critical patent/CN114933726A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0853—Vinylacetate
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/08—Homopolymers or copolymers of vinylidene chloride
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—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 a halogen; Derivatives of such polymers
    • C08J2427/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/04—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2427/08—Homopolymers or copolymers of vinylidene chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • 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
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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Abstract

The invention provides a high-barrier composite film and a preparation method thereof, belonging to the technical field of new materials. It has solved the problem that prior art has the preparation process security poor. The high-barrier composite film comprises a bottom layer, a middle layer and a surface layer, wherein the bottom layer is one or more of a polypropylene film, a polyethylene film, a biaxially oriented polyester film and a biaxially oriented polyamide film, and the middle layer is one or more of waterborne acrylic acid, waterborne polyurethane and waterborne polyvinyl alcohol; the surface layer is one or more of PVDC emulsion and PVA emulsion, the middle layer is positioned between the bottom layer and the surface layer, and the surface layer is stably connected to the bottom layer under the action of the middle layer. The preparation method of the high-barrier composite film comprises the following steps: A. preparing; B. carrying out corona treatment; C. and (4) connecting. The high-barrier composite membrane is environment-friendly and safe, and the preparation method does not discharge toxic gas.

Description

High-barrier composite film and preparation method thereof
Technical Field
The invention belongs to the technical field of new materials, and relates to a high-barrier composite film and a preparation method thereof.
Background
The high barrier film coating film has excellent barrier property and is mainly used for food packaging.
The binder of the current coating film is solvent-based, namely: the diluent (ethyl acetate) used in the polyurethane adhesive can release a large amount of toxic gas and other toxic chemical components in the production process, so that the environment is harmed, and the health of operators is influenced. Moreover, the product also presents a quality safety risk due to solvent residues.
In addition, the diluent ethyl acetate is a flammable and explosive chemical, and has potential safety hazard when the concentration reaches the explosion limit range.
Chinese patent publication No. CN1687264 provides a method for manufacturing a modified polyvinyl alcohol high-barrier coating film and the polyvinyl alcohol high-barrier coating film manufactured by the method, PVOH is used as a raw material, is catalyzed and then is modified, and is added with an auxiliary agent to prepare a coating which is coated on a base material film to form the high-barrier coating film. After partial catalytic condensation, the molecular chain of PVOH reduces the acting force of hydrogen bonds in the molecule, greatly improves the water resistance of the PVOH, and solves the problem that the PVOH loses the barrier property in a wet state.
However, the above patent directly coats PVOH raw material on the substrate, which is poor in connection stability.
Disclosure of Invention
A first object of the present invention is to provide a high barrier composite film having high safety and high barrier properties, in view of the above problems of the prior art.
The second purpose of the invention is to provide a preparation method of the high-barrier composite film.
The first object of the present invention can be achieved by the following technical solutions:
a high-barrier composite film comprises a bottom layer, a middle layer and a surface layer, and is characterized in that the bottom layer is one or more of a polypropylene film, a polyethylene film, a biaxially oriented polyester film and a biaxially oriented polyamide film, and the middle layer is one or more of waterborne acrylic acid, waterborne polyurethane and waterborne polyvinyl alcohol; the surface layer is one or more of PVDC emulsion and PVA emulsion, the middle layer is positioned between the bottom layer and the surface layer, and the surface layer is stably connected to the bottom layer under the action of the middle layer.
Because the middle layer is a water-based adhesive, the whole production process of the high-barrier composite membrane does not contain ethyl acetate and other chemical solvents, and the diluent used for the middle layer is soft water. Zero discharge of VOC, safe and environment-friendly production process and low cost.
Certainly, the adhesive force between the surface layer and the bottom layer can be effectively improved under the action of the middle layer, and meanwhile, under the characteristic of the surface layer, the temperature resistance and the barrier property of the whole high-barrier composite film are good.
The second object of the present invention can be achieved by the following technical solutions:
a preparation method of a high-barrier composite film, the high-barrier composite film comprises a bottom layer, a middle layer and a surface layer, the middle layer is connected between the bottom layer and the surface layer, and the preparation method is characterized by comprising the following steps:
A. preparing:
firstly, a bottom layer: one or more of polypropylene particles, polyethylene particles, biaxially oriented polyester particles and biaxially oriented polyamide particles are extruded and cast in a hot melting state, and the bottom layer of the organic film is obtained by rolling and stretching;
II, an intermediate layer: uniformly stirring one or more of waterborne acrylic acid, waterborne polyurethane and waterborne polyvinyl alcohol;
thirdly, surface layer: mixing one or more of PVDC emulsion and PVA emulsion;
B. corona treatment: connecting the bottom layer to the unreeling operation position of a coating machine, carrying out corona treatment on the bottom layer, and enabling the surface tension of the treated bottom layer to be 38-50 mN/m;
C. connecting: and uniformly coating the middle layer on the bottom layer, drying, stably connecting the middle layer with the bottom layer, coating the surface layer on the middle layer, drying, cooling and rolling to obtain the high-barrier composite membrane.
The bottom layer, the middle layer and the surface layer are prepared independently, and the bottom layer is firstly subjected to corona treatment on a coating machine to ensure the surface tension of the bottom layer. And then coating the middle layer on the bottom layer, and drying to obtain the stable connection between the bottom layer and the middle layer.
And coating the bottom layer on the middle layer, and stably connecting the dried bottom layer, the middle layer and the surface layer.
In the preparation method of the high-barrier composite film, the middle bottom layer and the middle layer in the step C are connected and then are preheated, and then are put into an oven to be dried, so that a primary semi-finished product is obtained.
And drying treatment is carried out after preheating treatment, so that crack gaps can be avoided in the middle layer.
In the preparation method of the high-barrier composite film, the preheating temperature of the primary semi-finished product is 90-100 ℃.
In the preparation method of the high-barrier composite film, the drying environment temperature of the primary semi-finished product is 70-80 ℃.
In the above method for preparing a high barrier composite film, the primary semi-finished product is cooled after the step C.
In the preparation method of the high-barrier composite film, in the step C, after the surface layer is connected with the intermediate layer, preheating treatment is firstly carried out, and then the surface layer and the intermediate layer are placed in an oven for drying treatment, so that a secondary semi-finished product is obtained.
And drying treatment is carried out after preheating treatment, so that crack gaps can be avoided on the surface layer.
In the preparation method of the high-barrier composite film, the preheating temperature of the secondary semi-finished product is 90-100 ℃.
In the preparation method of the high-barrier composite film, the drying environment temperature of the secondary semi-finished product is 100-110 ℃.
In the above method for preparing a high barrier composite film, the secondary semi-finished product is cooled after the step C.
In the preparation method of the high-barrier composite film, after the step E, the high-barrier composite film is placed in a curing chamber at 45-50 ℃ for curing, the curing time is 48-72 hours, and the high-barrier composite film is conveyed and then cut and put into a warehouse.
The molecular weight can be increased by times through curing treatment to generate a net-shaped cross-linked structure, so that the composite material has higher composite fastness, better heat resistance and stability against medium erosion.
Compared with the prior art, the high-barrier composite membrane adopts the water-based solvent as the middle layer, so that the whole high-barrier composite membrane has no toxic gas in the preparation process and after the preparation is finished, and the safety is higher.
Meanwhile, all layers of the whole high-barrier composite membrane are stably attached, the barrier property is good, and the high-barrier composite membrane has high practical value.
Drawings
Fig. 1 is a schematic structural view of the high-barrier composite membrane.
In the figure, 1, the bottom layer; 2. an intermediate layer; 3. a skin layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It will be understood that when an element is referred to as being "mounted on" another element, it can be directly mounted on the other element or intervening elements may also be present. When a component is referred to as being "disposed on" another component, it can be directly on the other component or intervening components may also be present. When an element is referred to as being "secured to" another element, it can be directly secured to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "or/and" includes any and all combinations of one or more of the associated listed items.
Example one
As shown in fig. 1, the high-barrier composite film comprises a bottom layer 1, an intermediate layer 2 and a surface layer 3, wherein the bottom layer 1 is one or more of a polypropylene film, a polyethylene film, a biaxially-oriented polyester film and a biaxially-oriented polyamide film, and the intermediate layer 2 is one or more of waterborne acrylic acid, waterborne polyurethane and waterborne polyvinyl alcohol; the surface layer 3 is one or more of PVDC emulsion and PVA emulsion, the middle layer 2 is positioned between the bottom layer 1 and the surface layer 3, and the surface layer 3 is stably connected on the bottom layer 1 under the action of the middle layer 2.
The high-barrier composite film comprises a bottom layer 1, a middle layer 2 and a surface layer 3, wherein the middle layer 2 is connected between the bottom layer 1 and the surface layer 3, and the preparation method of the high-barrier composite film comprises the following steps:
A. preparing:
firstly, a bottom layer: one or more of polypropylene particles, polyethylene particles, biaxially oriented polyester particles and biaxially oriented polyamide particles are extruded and cast in a hot melting state, and the bottom layer of the organic film is obtained by rolling and stretching;
II, an intermediate layer: uniformly stirring one or more of waterborne acrylic acid, waterborne polyurethane and waterborne polyvinyl alcohol;
thirdly, surface layer: mixing one or more of PVDC emulsion and PVA emulsion;
B. corona treatment: connecting the bottom layer to the unreeling operation position of a coating machine, carrying out corona treatment on the bottom layer, and obtaining the surface tension of the bottom layer after the treatment, wherein the surface tension of the bottom layer is 38 mN/m;
C. connecting: and uniformly coating the middle layer 2 on the bottom layer 1, drying, stably connecting the middle layer 2 with the bottom layer 1, coating the surface layer 3 on the middle layer 2, drying, cooling and rolling to obtain the high-barrier composite film.
And C, after the middle layer 1 and the middle layer 2 are connected, preheating is firstly carried out, and then the obtained product is placed into a drying oven to be dried, so that a primary semi-finished product is obtained. In this embodiment, the preheating temperature of the primary semi-finished product is 90 ℃. The drying environment temperature of the primary semi-finished product is 70 ℃.
And C, cooling the primary semi-finished product.
And C, after the surface layer 3 is connected with the middle layer 2, preheating is carried out, and then the surface layer and the middle layer are placed into an oven to be dried, so that a secondary semi-finished product is obtained. In this embodiment, the preheating temperature of the secondary semi-finished product is 90 ℃. And the drying environment temperature of the secondary semi-finished product is 100 ℃.
And C, cooling the secondary semi-finished product.
And E, placing the high-barrier composite film in a curing chamber at 45 ℃ for curing for 48 hours, and conveying the high-barrier composite film, and then cutting and warehousing the high-barrier composite film.
Because the middle layer is a water-based adhesive, the whole production process of the high-barrier composite membrane does not contain chemical solvents such as ethyl acetate and the like, and the diluent used for the middle layer is soft water. Zero emission of VOC, safe and environment-friendly production process and low cost.
Certainly, the adhesive force between the surface layer and the bottom layer can be effectively improved under the action of the middle layer, and meanwhile, under the characteristic of the surface layer, the temperature resistance and the barrier property of the whole high-barrier composite film are good.
In this embodiment, the bottom layer is a polypropylene film, and the peel strength of the entire high-barrier composite film is 1.5N/15 mm. The water vapor transmission rate is 6.0g/(m2.24h), and the oxygen transmission rate is 15cm 3/(m2.24h).
Example two
As shown in fig. 1, the high-barrier composite film comprises a bottom layer 1, an intermediate layer 2 and a surface layer 3, wherein the bottom layer 1 is one or more of a polypropylene film, a polyethylene film, a biaxially oriented polyester film and a biaxially oriented polyamide film, and the intermediate layer 2 is one or more of waterborne acrylic acid, waterborne polyurethane and waterborne polyvinyl alcohol; the surface layer 3 is one or more of PVDC emulsion and PVA emulsion, the middle layer 2 is positioned between the bottom layer 1 and the surface layer 3, and the surface layer 3 is stably connected on the bottom layer 1 under the action of the middle layer 2.
The high-barrier composite film comprises a bottom layer 1, a middle layer 2 and a surface layer 3, wherein the middle layer 2 is connected between the bottom layer 1 and the surface layer 3, and the preparation method of the high-barrier composite film comprises the following steps:
A. preparing:
firstly, a bottom layer: one or more of polypropylene particles, polyethylene particles, biaxially oriented polyester particles and biaxially oriented polyamide particles are extruded and cast in a hot melting state, and the bottom layer of the organic film is obtained by rolling and stretching;
II, an intermediate layer: uniformly stirring one or more of waterborne acrylic acid, waterborne polyurethane and waterborne polyvinyl alcohol;
thirdly, surface layer: mixing one or more of PVDC emulsion and PVA emulsion;
B. corona treatment: connecting the bottom layer to the unreeling operation position of a coating machine, carrying out corona treatment on the bottom layer, and enabling the surface tension of the treated bottom layer to be 40 mN/m;
C. connecting: and uniformly coating the middle layer 2 on the bottom layer 1, drying, stably connecting the middle layer 2 with the bottom layer 1, coating the surface layer 3 on the middle layer 2, drying, cooling and rolling to obtain the high-barrier composite film.
And C, after the middle layer 1 and the middle layer 2 are connected, preheating is firstly carried out, and then the obtained product is placed into an oven for drying treatment, so that a primary semi-finished product is obtained. In this embodiment, the preheating temperature of the primary semi-finished product is 100 ℃. And the drying environment temperature of the primary semi-finished product is 80 ℃.
And C, cooling the primary semi-finished product.
And C, after the surface layer 3 is connected with the middle layer 2, preheating is carried out, and then the surface layer and the middle layer are placed into an oven to be dried, so that a secondary semi-finished product is obtained. In this embodiment, the preheating temperature of the secondary semi-finished product is 100 ℃. And the drying environment temperature of the secondary semi-finished product is 110 ℃.
And C, cooling the secondary semi-finished product.
And E, placing the high-barrier composite film in a curing chamber at 50 ℃ for curing for 72 hours, and conveying, cutting and warehousing.
Because the middle layer is a water-based adhesive, the whole production process of the high-barrier composite membrane does not contain chemical solvents such as ethyl acetate and the like, and the diluent used for the middle layer is soft water. Zero discharge of VOC, safe and environment-friendly production process and low cost.
Certainly, the adhesive force between the surface layer and the bottom layer can be effectively improved under the action of the middle layer, and meanwhile, under the self characteristic of the surface layer, the whole high-barrier composite film is good in temperature resistance and barrier property.
In the embodiment, the bottom layer is a biaxially oriented polyester film, and the peel strength of the whole high-barrier composite film is 2.3N/15 mm. The water vapor transmission rate is 13.0g/(m2.24h), and the oxygen transmission rate is 12cm 3/(m2.24h).
EXAMPLE III
As shown in fig. 1, the high-barrier composite film comprises a bottom layer 1, an intermediate layer 2 and a surface layer 3, wherein the bottom layer 1 is one or more of a polypropylene film, a polyethylene film, a biaxially-oriented polyester film and a biaxially-oriented polyamide film, and the intermediate layer 2 is one or more of waterborne acrylic acid, waterborne polyurethane and waterborne polyvinyl alcohol; the surface layer 3 is one or more of PVDC emulsion and PVA emulsion, the middle layer 2 is positioned between the bottom layer 1 and the surface layer 3, and the surface layer 3 is stably connected on the bottom layer 1 under the action of the middle layer 2.
The high-barrier composite film comprises a bottom layer 1, a middle layer 2 and a surface layer 3, wherein the middle layer 2 is connected between the bottom layer 1 and the surface layer 3, and the preparation method of the high-barrier composite film comprises the following steps:
A. preparing:
firstly, a bottom layer: one or more of polypropylene particles, polyethylene particles, biaxially oriented polyester particles and biaxially oriented polyamide particles are extruded and cast in a hot melting state, and the bottom layer of the organic film is obtained by rolling and stretching;
II, an intermediate layer: uniformly stirring one or more of waterborne acrylic acid, waterborne polyurethane and waterborne polyvinyl alcohol;
thirdly, surface layer: mixing one or more of PVDC emulsion and PVA emulsion;
B. corona treatment: connecting the bottom layer to the unreeling operation position of the coating machine, carrying out corona treatment on the bottom layer, and obtaining the surface tension of 39mN/m of the treated bottom layer;
C. connecting: and uniformly coating the middle layer 2 on the bottom layer 1, drying, stably connecting the middle layer 2 with the bottom layer 1, coating the surface layer 3 on the middle layer 2, drying, cooling and rolling to obtain the high-barrier composite film.
And C, after the middle layer 1 and the middle layer 2 are connected, preheating is firstly carried out, and then the obtained product is placed into a drying oven to be dried, so that a primary semi-finished product is obtained. In this embodiment, the preheating temperature of the primary semi-finished product is 95 ℃. The drying environment temperature of the primary semi-finished product is 77 ℃.
And C, cooling the primary semi-finished product.
And C, after the surface layer 3 is connected with the middle layer 2, preheating is carried out, and then the surface layer and the middle layer are placed into an oven to be dried, so that a secondary semi-finished product is obtained. In this embodiment, the preheating temperature of the secondary semi-finished product is 95 ℃. And the drying environment temperature of the secondary semi-finished product is 103 ℃.
And C, cooling the secondary semi-finished product.
And E, placing the high-barrier composite film in a curing chamber at 46 ℃ for curing for 50 hours, and conveying the high-barrier composite film, and then cutting and warehousing the high-barrier composite film.
Because the middle layer is a water-based adhesive, the whole production process of the high-barrier composite membrane does not contain chemical solvents such as ethyl acetate and the like, and the diluent used for the middle layer is soft water. Zero emission of VOC, safe and environment-friendly production process and low cost.
Certainly, the adhesive force between the surface layer and the bottom layer can be effectively improved under the action of the middle layer, and meanwhile, under the self characteristic of the surface layer, the whole high-barrier composite film is good in temperature resistance and barrier property.
In the embodiment, the bottom layer is a biaxially oriented polyamide film, and the peel strength of the whole high-barrier composite film is 3.2N/15 mm. The water vapor transmission rate is 15.0g/(m2.24h), and the oxygen transmission rate is 10cm 3/(m2.24h).
The features of the above-described embodiments may be arbitrarily combined, and for the sake of brevity, all possible combinations of the features in the above-described embodiments are not described, but should be construed as being within the scope of the present disclosure as long as there is no contradiction between the combinations of the features.
It should be understood by those skilled in the art that the above embodiments are only for illustrating the present invention and are not to be used as a limitation of the present invention, and that suitable changes and modifications to the above embodiments are within the scope of the claimed invention as long as they are within the spirit of the present invention.

Claims (10)

1. A high-barrier composite film comprises a bottom layer, a middle layer and a surface layer, and is characterized in that the bottom layer is one or more of a polypropylene film, a polyethylene film, a biaxially oriented polyester film and a biaxially oriented polyamide film, and the middle layer is one or more of waterborne acrylic acid, waterborne polyurethane and waterborne polyvinyl alcohol; the surface layer is one or more of PVDC emulsion and PVA emulsion, the middle layer is positioned between the bottom layer and the surface layer, and the surface layer is stably connected to the bottom layer under the action of the middle layer.
2. A preparation method of a high-barrier composite film, the high-barrier composite film comprises a bottom layer, a middle layer and a surface layer, the middle layer is connected between the bottom layer and the surface layer, and the preparation method is characterized by comprising the following steps:
A. preparing:
firstly, a bottom layer: one or more of polypropylene particles, polyethylene particles, biaxially oriented polyester particles and biaxially oriented polyamide particles are extruded and cast in a hot-melt state, and the bottom layer of the organic film is obtained by rolling and stretching;
II, an intermediate layer: uniformly stirring one or more of waterborne acrylic acid, waterborne polyurethane and waterborne polyvinyl alcohol;
thirdly, surface layer: mixing one or more of PVDC emulsion and PVA emulsion;
B. corona treatment: connecting the bottom layer to the unreeling operation position of a coating machine, carrying out corona treatment on the bottom layer, and enabling the surface tension of the treated bottom layer to be 38-40 mN/m;
C. connecting: and uniformly coating the middle layer on the bottom layer, drying, stably connecting the middle layer with the bottom layer, coating the surface layer on the middle layer, drying, cooling and rolling to obtain the high-barrier composite membrane.
3. The method for preparing the high-barrier composite film according to claim 2, wherein in the step C, the bottom layer and the middle layer are connected and then are subjected to preheating treatment, and then the bottom layer and the middle layer are placed into an oven to be dried, so that a primary semi-finished product is obtained.
4. The method for preparing the high-barrier composite film according to claim 3, wherein the preheating temperature of the primary semi-finished product is 90-100 ℃.
5. The method for preparing a high-barrier composite film according to claim 4, wherein the drying ambient temperature of the primary semi-finished product is 70-80 ℃.
6. The method for preparing a high-barrier composite film according to claim 5, wherein the primary semi-finished product is cooled after the step C.
7. The method for preparing the high-barrier composite film according to claim 6, wherein in the step C, the surface layer and the middle layer are connected and then are subjected to preheating treatment, and then are put into an oven for drying treatment, so that a secondary semi-finished product is obtained.
8. The method for preparing the high-barrier composite film according to claim 7, wherein the preheating temperature of the secondary semi-finished product is 90-100 ℃.
9. The method for preparing a high-barrier composite film according to claim 8, wherein the drying ambient temperature of the secondary semi-finished product is 100-110 ℃.
10. The method for preparing a high-barrier composite film according to claim 9, wherein the secondary semi-finished product is subjected to a cooling treatment after the step C.
CN202210470779.8A 2022-04-28 2022-04-28 High-barrier composite film and preparation method thereof Pending CN114933726A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5942320A (en) * 1996-09-03 1999-08-24 Daicel Chemical Industries, Ltd. Barrier composite films and a method for producing the same
CN110654090A (en) * 2019-09-24 2020-01-07 海南赛诺实业有限公司 High-barrier and high-peel-strength PVOH (polyvinyl alcohol) coating film and manufacturing method thereof
CN113910729A (en) * 2021-11-03 2022-01-11 海南赛诺实业有限公司 High-heat-seal-strength biaxially oriented polypropylene high-barrier coating film and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5942320A (en) * 1996-09-03 1999-08-24 Daicel Chemical Industries, Ltd. Barrier composite films and a method for producing the same
CN110654090A (en) * 2019-09-24 2020-01-07 海南赛诺实业有限公司 High-barrier and high-peel-strength PVOH (polyvinyl alcohol) coating film and manufacturing method thereof
CN113910729A (en) * 2021-11-03 2022-01-11 海南赛诺实业有限公司 High-heat-seal-strength biaxially oriented polypropylene high-barrier coating film and preparation method thereof

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Title
李颜霞编著, 北京：化学工业出版社 *

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Application publication date: 20220823