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CN110561885A - Preparation method of high-barrier flexible aluminized film - Google Patents

Preparation method of high-barrier flexible aluminized film Download PDF

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Publication number
CN110561885A
CN110561885A CN201910810875.0A CN201910810875A CN110561885A CN 110561885 A CN110561885 A CN 110561885A CN 201910810875 A CN201910810875 A CN 201910810875A CN 110561885 A CN110561885 A CN 110561885A
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film
preparation
aluminizer
barrier flexible
zein
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李魁
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/162—Cleaning
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0064—Smoothing, polishing, making a glossy surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/24—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/12—Paper, e.g. cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
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  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a preparation method of a high-barrier flexible aluminizer, belonging to the technical field of packaging materials. According to the invention, zein and polyurethane jointly modified polyethylene resin are used as an adhesive, ion-assisted thermal evaporation composite magnetron sputtering coating equipment is adopted, a priming layer is firstly subjected to magnetron sputtering, then ion-assisted thermal evaporation is carried out, a pure aluminum composite film layer is prepared, the pure aluminum composite film layer is subjected to polishing and anodic oxidation treatment, and then is subjected to wet-type compounding with paperboard to prepare a high-barrier flexible aluminum-plated film; according to the invention, polyether or polyester polyol reacts with diisocyanate and the like to generate a prepolymer with isocyanate group (-NCO), the prepolymer and water in the air or the surface of an adherend are utilized to generate better bonding strength, zein and polyurethane are jointly used to modify polyethylene resin as an adhesive, and secondary amine groups in zein and hydroxymethyl groups in polyurethane are subjected to a crosslinking reaction under a heated condition, so that the adhesive force of an aluminizer is enhanced.

Description

Preparation method of high-barrier flexible aluminized film
Technical Field
The invention relates to a preparation method of a high-barrier flexible aluminizer, belonging to the technical field of packaging materials.
Background
The aluminizer is a bright metal color film formed by evaporating high-purity aluminum wires into a gaseous state at a high temperature (110-1200 ℃) through a vacuum aluminizing process, and then precipitating gaseous aluminum atoms on the surface of a plastic film when the plastic film passes through a vacuum evaporation chamber. The aluminizing film is a composite flexible package material formed by plating a layer of extremely thin metal aluminum on the surface of a plastic film by adopting a special process, wherein the most common processing method is a multi-level vacuum aluminizing method, namely, the metal aluminum is melted and evaporated at high temperature in a high vacuum state, so that the vapor of the aluminum is deposited and accumulated on the surface of the plastic film, and the surface of the plastic film has metal luster.
The most used aluminum-plated films at present are mainly polyester aluminum-plated film (VMPET) and CPP aluminum-plated film (VMCPP). The aluminizing film has the functions of shading and preventing ultraviolet irradiation, not only prolongs the quality guarantee period of contents, but also improves the brightness of the film, replaces aluminum foil to a certain extent, and has low price, attractive appearance and better barrier property, so the aluminizing film has wide application in composite packaging and is mainly applied to dry and puffed food packaging such as biscuits and the like and external packaging of some medicines and cosmetics. At present, PET and BOPP (biaxially oriented polypropylene) are mainly selected as aluminized film base materials in the label industry on the market.
However, the BOPP aluminized film widely used in the market at present is processed by aluminizing conventional BOPP, but the fastness of aluminizing layer can only reach the level of 85% -90% non-peeling (i.e. the peeling rate reaches 10% -15%) when the 3M-610 adhesive tape is torn and torn, namely the 3M-610 adhesive tape is a transparent BOPP pressure-sensitive adhesive tape which meets the national industrial standard that the peeling strength in 6.12.1 of aluminized film BB/T0030-2004 for packaging is (2.0 +/-0.2) N/cm, namely the peeling strength between the inner layer and the secondary inner layer after the polyester aluminized film is compounded with other materials is not less than 1.0N/15mm (the national medical standard that the peeling strength between the inner layer and the secondary inner layer is specified in YY0236-1996 for medicine packaging is quite different from that of 4.4 th strip in the national medical industry standard that after the common BOPP aluminized film is compounded with other materials at present, the peeling strength between the aluminized layer and the secondary outer layer is not more than 0.5N/15mm basically, therefore, the application and the application range of the BOPP aluminized film are greatly limited. And the heat-sealing layer of the existing aluminizer has higher temperature and poor toughness, when the aluminizer is applied to commodity packaging, oxygen is easy to permeate into the heat-sealing part, the oxygen barrier property is poor, and the problem of poor adhesion of the aluminizer seriously restricts the large-scale popularization and application of the aluminizer. How to effectively enhance the adhesion property, toughness and barrier property of the aluminizer becomes a problem to be solved urgently in the whole printing and packaging industry.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problems that the existing aluminizer has poor adhesive force and seriously restricts the large-scale popularization and application of the aluminizer, the preparation method of the high-barrier flexible aluminizer is provided.
in order to solve the technical problems, the invention adopts the technical scheme that:
(1) Mixing polyethylene glycol, diisocyanate, zein, polyethylene resin and dibutyltin dilaurate, stirring and reacting to obtain a reactant A, adding the zein and the polyethylene resin into the reactant A, stirring at a constant temperature of 500-600 r/min for 1-2 h to obtain a reactant B, adding the dibutyltin dilaurate into the reactant B, continuously stirring for 20-30 min to obtain a mixed material, and carrying out vacuum defoaming treatment on the mixed material to obtain a binder;
(2) 45 steel with the thickness of 45mm, the thickness of 25mm and the thickness of 2mm are selected as a substrate, a pure aluminum target with the purity of 99.5% is selected as a target, the purity of an evaporation aluminum wire is 99.5%, the substrate is polished by water sand paper, then ultrasonic cleaning is respectively carried out for 3-5 min by acetone and absolute ethyl alcohol, natural drying is carried out, a pretreatment substrate is obtained, the pretreatment substrate is placed in a coating machine, ion cleaning is carried out, a cleaning substrate is obtained, and a pure aluminum film layer is obtained after sputtering film forming;
(3) Mixing H according to the volume ratio of 1: 44ClO4mixing with anhydrous ethanolMixing to obtain polishing solution, polishing the pure aluminum film layer to obtain a polished film, and performing primary anodic oxidation on the polished film to obtain a primary oxide film; carrying out secondary anodic oxidation on the primary oxide film to obtain a secondary oxide film;
(4) And (3) uniformly coating a binder on the surface of the paperboard, and compounding the secondary oxide film on the surface of the paperboard for pressing treatment to obtain the high-barrier flexible aluminizer.
The proportions of the polyethylene glycol, the diisocyanate, the zein, the polyethylene resin and the dibutyltin dilaurate in the step (1) are respectively as follows: respectively weighing 10-20 parts of polyethylene glycol, 30-40 parts of diisocyanate, 10-15 parts of zein, 40-60 parts of polyethylene resin and 1-3 parts of dibutyltin dilaurate in parts by weight.
The stirring reaction step in the step (1) is as follows: mixing polyethylene glycol and diisocyanate, and stirring and reacting for 2-3 hours at the temperature of 70-80 ℃ and the stirring speed of 300-400 r/min.
The vacuum defoaming treatment step in the step (1) is as follows: and (3) carrying out vacuum defoaming on the mixed material at the temperature of 110-120 ℃ for 30-40 min.
The ion cleaning step in the step (2) is as follows: and placing the pretreated substrate in a coating machine, and carrying out ion cleaning for 10-20 min at the temperature of 90-100 ℃ and under the negative bias voltage of 800V and 2 Pa.
The sputtering film forming step in the step (2) is as follows: under vacuum degree of 3X 10-3～5×10-3and (3) evaporating for 10-15 min under the condition that the evaporation power is 18-20 kW after sputtering film forming under Pa.
The polishing treatment step in the step (3) is as follows: and (3) placing the pure aluminum film layer into polishing solution, and polishing for 3-5 min at the voltage of 16-18V and the temperature of 10-15 ℃.
the primary anodic oxidation step in the step (3) is as follows: soaking the polishing film in sulfuric acid with the mass fraction of 15%, anodizing for 1-2 hours under the voltage of 15-20V, and then carrying out 6% H mass fraction with the volume ratio of 1: 13PO4And 1.8% by mass of H2CrO4Washing the mixed solution for 3-5 times.
The secondary anodic oxidation step in the step (3) is as follows: soaking the primary oxide film in sulfuric acid with the mass fraction of 15%, and carrying out secondary anodic oxidation for 1-2 hours at the voltage of 20-25V and the temperature of 0-3 ℃.
The pressing treatment step in the step (4) is as follows: and (3) uniformly coating a binder on the surface of the paperboard, compounding the secondary oxide film on the surface of the paperboard, and pressing for 3-5 min under the pressure of 3-5 MPa.
Compared with other methods, the method has the beneficial technical effects that:
(1) according to the invention, zein and polyurethane jointly modified polyethylene resin are used as an adhesive, ion-assisted thermal evaporation composite magnetron sputtering coating equipment is adopted, a priming layer is firstly subjected to magnetron sputtering, then ion-assisted thermal evaporation is carried out, a pure aluminum composite film layer is prepared, the pure aluminum composite film layer is subjected to polishing and anodic oxidation treatment, and then is subjected to wet-type compounding with paperboard to prepare a high-barrier flexible aluminum-plated film; the secondary amine group in the zein can perform a crosslinking reaction with hydroxymethyl in the polyurethane under a heated condition, so that the bonding strength and the water resistance can be improved; after the pure aluminium composite film layer is undergone the process of anodic oxidation treatment, the grain boundary has higher free energy and a certain tension action due to the enrichment of excessive impurity and defect, and the pore-forming at this place and pore-forming in the grain are obviously different, in the course of secondary anodic oxidation, H is used3PO4And H4CrO4The mixed solution of the method is used for dissolving the primary anodic oxide film with poor orderliness, and then a periodic pit interface with more orderliness is left on the surface of the pure aluminum base, and the pit-shaped interface generates 'induction' on the electric field distribution in the secondary anodic oxidation process, so that the ordered porous aluminizer can be obtained at the beginning of film formation when the porous film is prepared by the secondary anodic oxidation method, and a long-time self-organization process is not needed; the ordered pore arrangement range of the porous aluminized film prepared by the secondary corrosion method is limited within a range of a few or dozens of micrometers, and the ordered pore arrangement range depends on the size of sub-grains and the limited induction of the periodic pit-shaped interface on the capacity of an external electric field, so that the adhesive force of the aluminized film is improved;
(2) the zein is rich in sulfur-containing amino acid, and the protein molecules are connected by stronger disulfide bonds and hydrophobic bonds, which is the basis that the zein is easy to form a film, after coating film forming liquid, the film is dehydrated and dried along with the volatilization of ethanol, so that the concentration of the protein in the film forming liquid is increased, when the concentration exceeds a certain value, the protein is condensed, hydrogen bonds, disulfide bonds and hydrophobic bonds for maintaining the network structure of the film are formed among the molecules, and the zein film is formed; zein is insoluble in water, can be decomposed by microorganisms and protease, and has biodegradability and strong oxidation resistance to lipid;
(3) According to the invention, polyether or polyester polyol reacts with diisocyanate and the like to generate an isocyanate-terminated (-NCO) prepolymer, the prepolymer and water in the air or the surface of an adherend are utilized to generate better bonding strength, zein and polyurethane are jointly used to modify polyethylene resin as an adhesive, and secondary amine groups in zein and hydroxymethyl groups in polyurethane are subjected to a crosslinking reaction under a heated condition, so that the bonding strength of the polyethylene resin is improved, and the adhesive force of an aluminizer is enhanced.
Detailed Description
Respectively weighing 10-20 parts by weight of polyethylene glycol, 30-40 parts by weight of diisocyanate, 10-15 parts by weight of zein, 40-60 parts by weight of polyethylene resin and 1-3 parts by weight of dibutyltin dilaurate, mixing the polyethylene glycol and the diisocyanate, stirring and reacting for 2-3 hours at the temperature of 70-80 ℃ and the stirring speed of 300-400 r/min to obtain a reactant A, adding the zein and the polyethylene resin into the reactant A, stirring for 1-2 hours at the constant temperature of 500-600 r/min to obtain a reactant B, adding the dibutyltin dilaurate into the reactant B, continuously stirring for 20-30 minutes to obtain a mixed material, and carrying out vacuum deaeration on the mixed material at the temperature of 110-120 ℃ for 30-40 minutes to obtain a binder; selecting 45 steel with the thickness of 45mm multiplied by 25mm multiplied by 2mm as a substrate, selecting a pure aluminum target with the purity of 99.5% as a target material, evaporating aluminum wires with the purity of 99.5%, polishing the substrate by using water sand paper, respectively ultrasonically cleaning the substrate by using acetone and absolute ethyl alcohol for 3-5 min, naturally drying the substrate to obtain a pretreated substrate, placing the pretreated substrate in a film coating machine, and performing negative bias voltage of 800V and 2Pa at the temperature of 90-100 DEG Cion cleaning for 10-20 min to obtain cleaned matrix with vacuum degree of 3 × 10-3～5×10-3After sputtering under Pa to form a film, evaporating for 10-15 min under the condition that the evaporation power is 18-20 kW to obtain a pure aluminum film layer; mixing H according to the volume ratio of 1: 44ClO4Mixing with absolute ethyl alcohol to obtain polishing solution, placing the pure aluminum film layer in the polishing solution, polishing for 3-5 min at the temperature of 10-15 ℃ and the voltage of 16-18V to obtain a polishing film, soaking the polishing film in sulfuric acid with the mass fraction of 15%, anodizing for 1-2H at the voltage of 15-20V, and then carrying out anodic oxidation on the obtained product with the mass fraction of 6% H and the volume ratio of 1: 13PO4And 1.8% by mass of H2CrO4Washing the mixed solution for 3-5 times to obtain a primary oxide film; soaking the primary oxide film in sulfuric acid with the mass fraction of 15%, and carrying out secondary anodic oxidation for 1-2 hours at the voltage of 20-25V and the temperature of 0-3 ℃ to obtain a secondary oxide film; and (3) uniformly coating a binder on the surface of the paperboard, compounding the secondary oxide film on the surface of the paperboard, and pressing for 3-5 min under the pressure of 3-5 MPa to obtain the high-barrier flexible aluminizer.
Example 1
Respectively weighing 10 parts of polyethylene glycol, 30 parts of diisocyanate, 10 parts of zein, 40 parts of polyethylene resin and 1 part of dibutyltin dilaurate according to the parts by weight, mixing the polyethylene glycol and the diisocyanate, stirring and reacting for 2 hours at the temperature of 70 ℃ and the stirring speed of 300r/min to obtain a reactant A, adding the zein and the polyethylene resin into the reactant A, stirring for 1 hour at the constant temperature of 500r/min to obtain a reactant B, adding the dibutyltin dilaurate into the reactant B, continuously stirring for 20 minutes to obtain a mixed material, and carrying out vacuum deaeration on the mixed material for 30 minutes at the temperature of 110 ℃ to obtain the binder; selecting 45 steel with the thickness of 45mm multiplied by 25mm multiplied by 2mm as a substrate, selecting a pure aluminum target with the purity of 99.5% as a target material, evaporating aluminum wires with the purity of 99.5%, polishing the substrate by using water sand paper, respectively ultrasonically cleaning the substrate for 3min by using acetone and absolute ethyl alcohol, naturally airing to obtain a pretreated substrate, placing the pretreated substrate in a film coating machine, and carrying out ion cleaning for 10min at the temperature of 90 ℃, under the negative bias of 800V and 2Pa to obtain a cleaned substrate, wherein the vacuum degree is 3 multiplied by 10-3after sputtering under Pa to form a film, the film is evaporatedEvaporating at 18kW for 10min to obtain a pure aluminum film layer; mixing H according to the volume ratio of 1: 44ClO4Mixing with anhydrous ethanol to obtain polishing solution, placing pure aluminum film layer in the polishing solution, polishing at 10 deg.C and 16V for 3min to obtain polishing film, soaking the polishing film in 15% sulfuric acid, anodizing for 1 hr at 15V, and anodizing with 6% H at volume ratio of 1: 13PO4And 1.8% by mass of H2CrO4Washing the mixed solution for 3 times to obtain a primary oxide film; soaking the primary oxide film in sulfuric acid with the mass fraction of 15%, and carrying out secondary anodic oxidation for 1h at the voltage of 20V and the temperature of 0 ℃ to obtain a secondary oxide film; and (3) uniformly coating a binder on the surface of the paperboard, compounding the secondary oxide film on the surface of the paperboard, and pressing for 3min under the pressure of 3MPa to obtain the high-barrier flexible aluminizer.
Example 2
Respectively weighing 15 parts of polyethylene glycol, 35 parts of diisocyanate, 13 parts of zein, 50 parts of polyethylene resin and 2 parts of dibutyltin dilaurate according to the parts by weight, mixing the polyethylene glycol and the diisocyanate, stirring and reacting for 2.5 hours at the temperature of 75 ℃ and the stirring speed of 350r/min to obtain a reactant A, adding the zein and the polyethylene resin into the reactant A, stirring for 1.5 hours at the constant temperature of 550r/min to obtain a reactant B, adding the dibutyltin dilaurate into the reactant B, continuously stirring for 25 minutes to obtain a mixed material, and carrying out vacuum defoamation on the mixed material at the temperature of 115 ℃ for 35 minutes to obtain a binder; selecting 45 steel with the thickness of 45mm multiplied by 25mm multiplied by 2mm as a substrate, selecting a pure aluminum target with the purity of 99.5% as a target material, evaporating aluminum wires with the purity of 99.5%, polishing the substrate by using water sand paper, respectively ultrasonically cleaning the substrate for 4min by using acetone and absolute ethyl alcohol, naturally airing to obtain a pretreated substrate, placing the pretreated substrate in a film coating machine, and carrying out ion cleaning for 15min at the temperature of 95 ℃ and under the negative bias of 800V and 2Pa to obtain a cleaned substrate, wherein the vacuum degree is 4 multiplied by 10-3Sputtering under Pa to form a film, and evaporating for 13min under the evaporation power of 19kW to obtain a pure aluminum film layer; mixing H according to the volume ratio of 1: 44ClO4Mixing with anhydrous ethanol to obtain polishing solution, placing pure aluminum film layer in the polishing solution at 17 deg.Cv, polishing at the temperature of 13 ℃ for 4min to obtain a polishing film, soaking the polishing film in sulfuric acid with the mass fraction of 15%, anodizing for 1.5H at the voltage of 17V for the first time, and then carrying out H with the mass fraction of 6% and the volume ratio of 1: 13PO4And 1.8% by mass of H2CrO4Washing the mixed solution for 4 times to obtain a primary oxide film; soaking the primary oxide film in sulfuric acid with the mass fraction of 15%, and carrying out secondary anodic oxidation for 1.5h at the voltage of 23V and the temperature of 2 ℃ to obtain a secondary oxide film; and (3) uniformly coating a binder on the surface of the paperboard, compounding the secondary oxide film on the surface of the paperboard, and pressing for 4min under the pressure of 4MPa to obtain the high-barrier flexible aluminizer.
Example 3
Respectively weighing 20 parts of polyethylene glycol, 40 parts of diisocyanate, 15 parts of zein, 60 parts of polyethylene resin and 3 parts of dibutyltin dilaurate according to the parts by weight, mixing the polyethylene glycol and the diisocyanate, stirring and reacting for 3 hours at the temperature of 80 ℃ and the stirring speed of 400r/min to obtain a reactant A, adding the zein and the polyethylene resin into the reactant A, stirring for 2 hours at the constant temperature of 600r/min to obtain a reactant B, adding the dibutyltin dilaurate into the reactant B, continuously stirring for 30 minutes to obtain a mixed material, and carrying out vacuum defoaming on the mixed material at the temperature of 120 ℃ for 40 minutes to obtain a binder; selecting 45 steel with the thickness of 45mm multiplied by 25mm multiplied by 2mm as a substrate, selecting a pure aluminum target with the purity of 99.5% as a target material, evaporating aluminum wires with the purity of 99.5%, polishing the substrate by using water sand paper, respectively ultrasonically cleaning the substrate for 5min by using acetone and absolute ethyl alcohol, naturally airing to obtain a pretreated substrate, placing the pretreated substrate in a film coating machine, and carrying out ion cleaning for 20min at the temperature of 100 ℃ and under the negative bias of 800V and 2Pa to obtain a cleaned substrate, wherein the vacuum degree is 5 multiplied by 10-3Sputtering under Pa to form a film, and evaporating for 15min under the evaporation power of 20kW to obtain a pure aluminum film layer; mixing H according to the volume ratio of 1: 44ClO4mixing with anhydrous ethanol to obtain polishing solution, placing pure aluminum film layer in the polishing solution, polishing at 15 deg.C under 18V for 5min to obtain polishing film, soaking the polishing film in 15% sulfuric acid, anodizing for 2 hr under 20V, and anodizing at 1: 1 volume ratio to 6%H3PO4And 1.8% by mass of H2CrO4Washing the mixed solution for 5 times to obtain a primary oxide film; soaking the primary oxide film in sulfuric acid with the mass fraction of 15%, and carrying out secondary anodic oxidation for 2h at the voltage of 25V and the temperature of 3 ℃ to obtain a secondary oxide film; and (3) uniformly coating a binder on the surface of the paperboard, compounding the secondary oxide film on the surface of the paperboard, and pressing for 5min under the pressure of 5MPa to obtain the high-barrier flexible aluminizer.
The high-barrier flexible aluminizer prepared by the invention is detected, and the specific detection results are shown in the following table 1:
Comparative example: aluminum-plated film produced by Guangzhou company
And (3) performance testing:
(1) light-shielding property: and testing the light shading property of the high-barrier flexible aluminizer by adopting the full light transmittance.
And (3) aluminum plating layer adhesion force: the adhesion of the aluminum layer was tested.
And (3) toughness testing: puncture resistance times of 15N puncture by a puncture resistance instrument test without breakage are measured.
TABLE 1 characterization of high-barrier flexible aluminum-plated film
As can be seen from Table 1, the high-barrier flexible aluminum-plated film prepared by the invention has low light transmittance, strong adhesive force and good toughness, and solves the problem of poor adhesive force of the aluminum-plated film in the prior art.

Claims (10)

1. A preparation method of a high-barrier flexible aluminizer is characterized by comprising the following specific preparation steps:
(1) Mixing polyethylene glycol, diisocyanate, zein, polyethylene resin and dibutyltin dilaurate, stirring and reacting to obtain a reactant A, adding the zein and the polyethylene resin into the reactant A, stirring at a constant temperature of 500-600 r/min for 1-2 h to obtain a reactant B, adding the dibutyltin dilaurate into the reactant B, continuously stirring for 20-30 min to obtain a mixed material, and carrying out vacuum defoaming treatment on the mixed material to obtain a binder;
(2) 45 steel with the thickness of 45mm, the thickness of 25mm and the thickness of 2mm are selected as a substrate, a pure aluminum target with the purity of 99.5% is selected as a target, the purity of an evaporation aluminum wire is 99.5%, the substrate is polished by water sand paper, then ultrasonic cleaning is respectively carried out for 3-5 min by acetone and absolute ethyl alcohol, natural drying is carried out, a pretreatment substrate is obtained, the pretreatment substrate is placed in a coating machine, ion cleaning is carried out, a cleaning substrate is obtained, and a pure aluminum film layer is obtained after sputtering film forming;
(3) Mixing H according to the volume ratio of 1: 44ClO4Mixing with absolute ethyl alcohol to obtain polishing solution, polishing the pure aluminum film layer to obtain a polished film, and performing primary anodic oxidation on the polished film to obtain a primary oxide film; carrying out secondary anodic oxidation on the primary oxide film to obtain a secondary oxide film;
(4) And (3) uniformly coating a binder on the surface of the paperboard, and compounding the secondary oxide film on the surface of the paperboard for pressing treatment to obtain the high-barrier flexible aluminizer.
2. The preparation method of the high-barrier flexible aluminizer according to claim 1, characterized in that: the proportions of the polyethylene glycol, the diisocyanate, the zein, the polyethylene resin and the dibutyltin dilaurate in the step (1) are respectively as follows: respectively weighing 10-20 parts of polyethylene glycol, 30-40 parts of diisocyanate, 10-15 parts of zein, 40-60 parts of polyethylene resin and 1-3 parts of dibutyltin dilaurate in parts by weight.
3. The preparation method of the high-barrier flexible aluminizer according to claim 1, characterized in that: the stirring reaction step in the step (1) is as follows: mixing polyethylene glycol and diisocyanate, and stirring and reacting for 2-3 hours at the temperature of 70-80 ℃ and the stirring speed of 300-400 r/min.
4. The preparation method of the high-barrier flexible aluminizer according to claim 1, characterized in that: the vacuum defoaming treatment step in the step (1) is as follows: and (3) carrying out vacuum defoaming on the mixed material at the temperature of 110-120 ℃ for 30-40 min.
5. The preparation method of the high-barrier flexible aluminizer according to claim 1, characterized in that: the ion cleaning step in the step (2) is as follows: and placing the pretreated substrate in a coating machine, and carrying out ion cleaning for 10-20 min at the temperature of 90-100 ℃ and under the negative bias voltage of 800V and 2 Pa.
6. The preparation method of the high-barrier flexible aluminizer according to claim 1, characterized in that: the sputtering film forming step in the step (2) is as follows: under vacuum degree of 3X 10-3～5×10-3And (3) evaporating for 10-15 min under the condition that the evaporation power is 18-20 kW after sputtering film forming under Pa.
7. The preparation method of the high-barrier flexible aluminizer according to claim 1, characterized in that: the polishing treatment step in the step (3) is as follows: and (3) placing the pure aluminum film layer into polishing solution, and polishing for 3-5 min at the voltage of 16-18V and the temperature of 10-15 ℃.
8. The preparation method of the high-barrier flexible aluminizer according to claim 1, characterized in that: the primary anodic oxidation step in the step (3) is as follows: soaking the polishing film in sulfuric acid with the mass fraction of 15%, anodizing for 1-2 hours under the voltage of 15-20V, and then carrying out 6% H mass fraction with the volume ratio of 1: 13PO4And 1.8% by mass of H2CrO4Washing the mixed solution for 3-5 times.
9. The preparation method of the high-barrier flexible aluminizer according to claim 1, characterized in that: the secondary anodic oxidation step in the step (3) is as follows: soaking the primary oxide film in sulfuric acid with the mass fraction of 15%, and carrying out secondary anodic oxidation for 1-2 hours at the voltage of 20-25V and the temperature of 0-3 ℃.
10. the preparation method of the high-barrier flexible aluminizer according to claim 1, characterized in that: the pressing treatment step in the step (4) is as follows: and (3) uniformly coating a binder on the surface of the paperboard, compounding the secondary oxide film on the surface of the paperboard, and pressing for 3-5 min under the pressure of 3-5 MPa.
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WO2005014877A1 (en) * 2003-08-12 2005-02-17 Sandvik Intellectual Property Ab New metal strip product
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