CN116638842B - Composite aluminized film and preparation method thereof - Google Patents

Composite aluminized film and preparation method thereof Download PDF

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Publication number
CN116638842B
CN116638842B CN202310594889.XA CN202310594889A CN116638842B CN 116638842 B CN116638842 B CN 116638842B CN 202310594889 A CN202310594889 A CN 202310594889A CN 116638842 B CN116638842 B CN 116638842B
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polyethylene
layer
composite
melt index
10min
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CN116638842A (en
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林善华
张笋
陈永群
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Foshan Cailong Coating Packaging Materials Co ltd
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Foshan Cailong Coating Packaging Materials Co ltd
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • 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

Abstract

The application discloses a composite aluminizer and a preparation method thereof, and relates to the field of food packaging materials. The composite aluminizer comprises an MDOPE substrate layer, a PVA adhesive layer, an alumina layer and a PE inner layer which are sequentially arranged; the MDOPE substrate layer is obtained by melt blending a main material and an auxiliary agent, extruding and stretching in one direction. The main materials comprise linear low density polyethylene, chlorosulfonated polyethylene A and chlorosulfonated polyethylene B, wherein the weight ratio of the linear low density polyethylene to the chlorosulfonated polyethylene A to the chlorosulfonated polyethylene B is (60-70): (10-20): (10-20). The composite aluminized film can obtain excellent printing performance without corona treatment, and has high adhesion fastness among materials of each layer, good oxygen resistance and good steam resistance.

Description

Composite aluminized film and preparation method thereof
Technical Field
The application relates to the field of food packaging materials, in particular to a composite aluminizer and a preparation method thereof.
Background
The composite aluminized film is commonly used as a food packaging material and generally comprises a film substrate layer, an aluminum layer or an aluminum oxide layer and a heat sealing layer which are sequentially arranged, so that the barrier property of oxygen and water vapor can be improved, and the preservation time of food can be prolonged.
PE (polyethylene) is a thermoplastic resin prepared by ethylene polymerization, is nontoxic and has good chemical stability, and is mainly used for manufacturing films, packaging materials and the like. Among them, PE films include MDOPE films (biaxially oriented polyethylene films) and BOPE films (biaxially oriented polyethylene films). Compared with BOPE films, MDOPE films have low requirements on equipment, so that a plurality of manufacturers often adopt the MDOPE films as film substrate layers of composite aluminized films.
However, the MDOPE film in the related art generally has a problem of poor printing stability, which is unfavorable for the explanation of printed products, so that the composite aluminized film with the MDOPE film as a substrate layer in the related art generally has a problem of poor printing performance. However, increasing the corona treatment tends to introduce dirt, dust, etc. into the MDOPE film, and thus reduces the adhesion between the MDOPE film and other layer materials.
Disclosure of Invention
In order to solve the problems of poor printing performance and poor adhesion fastness among layer materials of the composite aluminizer in the related art, the application provides the composite aluminizer and a preparation method thereof.
In a first aspect, the present application provides a composite aluminizer, which adopts the following technical scheme:
a composite aluminizer comprises an MDOPE substrate layer, a PVA adhesive layer, an alumina layer and a PE inner layer which are sequentially arranged; the MDOPE substrate layer is obtained by carrying out melt blending on a main material and an auxiliary agent, and then extruding and unidirectional stretching;
the main materials comprise linear low density polyethylene, chlorosulfonated polyethylene A and chlorosulfonated polyethylene B, wherein the weight ratio of the linear low density polyethylene to the chlorosulfonated polyethylene A to the chlorosulfonated polyethylene B is (60-70): (10-20), wherein the linear low density polyethylene has a melt index in the range of 2.8-6.4g/10min, the chlorosulfonated polyethylene A has a melt index in the range of 0.3-1.2g/10min, and the chlorosulfonated polyethylene B has a melt index in the range of 2-3g/10min;
the auxiliary agent is selected from any one or a combination of a plurality of antioxidants, heat stabilizers and lubricants.
By adopting the technical scheme, the MDOPE substrate layer prepared by taking the linear low-density polyethylene, the chlorosulfonated polyethylene A and the chlorosulfonated polyethylene B as main materials has excellent printing performance without corona treatment. In addition, the combination of the linear low-density polyethylene, the chlorosulfonated polyethylene A and the chlorosulfonated polyethylene B within the specific melt index range can effectively improve the binding force between the MDOPE substrate layer and the PVA adhesive layer and improve the dimensional stability of the composite aluminized film.
Optionally, the melt index of the chlorosulfonated polyethylene A and the melt index of the chlorosulfonated polyethylene B are 1.5-1.8g/10min.
By adopting the technical scheme, when the melt indexes of chlorosulfonated polyethylene A and chlorosulfonated polyethylene B are 1.5-1.8g/10min, the adhesion fastness between the MDOPE substrate layer and the PVA adhesive layer can be effectively improved, and the dimensional stability of the composite aluminized film can be further improved.
Alternatively, the linear low density polyethylene has a melt index in the range of 3.8 to 4.6g/10min.
By adopting the technical scheme, when the melt index range of the linear low-density polyethylene is 3.8-4.6g/10min, the adhesion fastness between the MDOPE substrate layer and the PVA adhesive layer is further improved.
Optionally, the PE inner layer comprises metallocene polyethylene A, metallocene polyethylene B and low-density polyethylene, wherein the weight ratio of the metallocene polyethylene A to the metallocene polyethylene B to the low-density polyethylene is (3-4): (1-2): 10, the melt index of the metallocene polyethylene A ranges from 0.8g/10min to 1.5g/10min, the melt index of the metallocene polyethylene B ranges from 4.2g/10min to 6.8g/10min, and the melt index of the low-density polyethylene ranges from 1g/10min to 2g/10min.
By adopting the technical scheme, the PE inner layer prepared from the metallocene polyethylene A, the metallocene polyethylene B and the low-density polyethylene with the specific melt index range can improve the adhesion stability of the alumina layer and the PE inner layer on one hand, and can carry out heat sealing within the range of 100-140 ℃ on the other hand, and the heat sealing stability of the composite aluminized film is good within the heat sealing range.
Optionally, the melt index of the metallocene polyethylene A and the melt index of the metallocene polyethylene B are different by 4.5-5g/10min.
When the melt indexes of the metallocene polyethylene A and the metallocene polyethylene B are different by 4.5-5g/10min, the adhesion fastness between the materials of each layer is further improved, and the composite aluminized film with higher oxygen resistance and water vapor resistance is obtained. In addition, the method has a promoting effect on improving the dimensional stability of the composite aluminized film.
Optionally, the MDOPE substrate layer has a thickness of 18-25 μm.
Optionally, the thickness of the PVA adhesive layer is 1-2 μm.
Optionally, the thickness of the alumina layer is 300-500 angstroms.
Optionally, the thickness of the PE inner layer is 40-60 μm.
In a second aspect, the preparation method of any one of the composite aluminized films provided by the application adopts the following technical scheme: the preparation method of the composite aluminizer comprises the following steps:
feeding the PE inner layer into vacuum aluminizing equipment, heating an aluminum wire, introducing oxygen in the aluminum evaporation process, enabling the oxygen to react with gaseous aluminum to generate aluminum oxide, and depositing on one side of the PE inner layer through the action of physical vapor deposition to obtain an aluminum oxide layer to obtain a composite aluminum oxide film;
and coating a PVA adhesive layer on one side of the MDOPE substrate layer, and then immediately compounding the aluminum oxide layer of the composite aluminum oxide film with the PVA adhesive layer and drying to obtain the composite aluminum-plated film.
Firstly, aluminum oxide is plated on the PE inner layer to obtain a composite aluminum oxide film, and then the composite aluminum oxide film is compounded with the MDOPE base material layer, so that the flatness of the composite aluminum oxide film can be improved.
In summary, the technical scheme of the application at least comprises the following beneficial effects:
the MDOPE substrate layer is modified, and excellent printing performance can be obtained without corona treatment;
2. the adhesion fastness among the materials of each layer of the composite aluminizer is high, and the oxygen resistance and the water vapor resistance are good;
3. the composite aluminized film has high heat sealing strength and good dimensional stability.
Drawings
FIG. 1 is a schematic structural diagram of a composite aluminizer according to the present application.
Reference numerals illustrate:
1. an MDOPE substrate layer; 2. a PVA adhesive layer; 3. an alumina layer; 4. PE inner layer.
Detailed Description
The present application will be described in further detail with reference to specific examples, and comparative examples.
Preparation of MDOPE substrate layer
Preparation example 1
An MDOPE substrate layer comprises the following raw materials in parts by weight:
linear low density polyethylene: 70kg, melt index 3.8g/10min;
chlorosulfonated polyethylene a:10kg, melt index of 0.3g/10min and chlorine content of 10%;
chlorosulfonated polyethylene B:20kg, a melt index of 3g/10min and a chlorine content of 37%;
heat stabilizer: 3kg of calcium stearate is specifically selected;
and (3) a lubricant: 0.5kg of polyethylene wax is specifically selected.
In this preparation example, the preparation method of the MDOPE substrate layer is as follows:
uniformly mixing linear low-density polyethylene, chlorosulfonated polyethylene A, chlorosulfonated polyethylene B, a heat stabilizer and a lubricant, and then performing melt extrusion in an extruder, wherein the temperature of the extruder is set to 160-170 ℃ and the temperature of a die head is set to 170-180 ℃; and then cooling and longitudinally stretching after film blowing to form a film bubble to obtain the MDOPE substrate layer, wherein the temperature during longitudinal stretching is controlled to be 90-100 ℃, and the stretching ratio is controlled to be 2:1.
Preparation example 2
An MDOPE substrate layer comprises the following raw materials in parts by weight:
linear low density polyethylene: 60kg, melt index 4.6g/10min;
chlorosulfonated polyethylene a:20kg, a melt index of 1.2g/10min and a chlorine content of 15%;
chlorosulfonated polyethylene B:20kg, melt index of 2g/10min and chlorine content of 33%;
heat stabilizer: 2kg of calcium stearate is specifically selected;
and (3) a lubricant: 0.3kg of polyethylene wax is specifically selected.
In this preparation example, the preparation method of the MDOPE substrate layer comprises the following steps:
uniformly mixing linear low-density polyethylene, chlorosulfonated polyethylene A, chlorosulfonated polyethylene B, a heat stabilizer and a lubricant, and then performing melt extrusion in an extruder, wherein the temperature of the extruder is set to 160-170 ℃ and the temperature of a die head is set to 170-180 ℃; and then cooling and longitudinally stretching after film blowing to form a film bubble to obtain the MDOPE substrate layer, wherein the temperature during longitudinal stretching is controlled to be 90-100 ℃, and the stretching ratio is controlled to be 2:1.
Preparation example 3
An MDOPE substrate layer comprises the following raw materials in parts by weight:
linear low density polyethylene: 70kg, melt index 3.8g/10min;
chlorosulfonated polyethylene a:10kg, melt index of 0.5g/10min and chlorine content of 13%;
chlorosulfonated polyethylene B:20kg, melt index of 2g/10min and chlorine content of 33%;
heat stabilizer: 3kg of calcium stearate is specifically selected;
and (3) a lubricant: 0.5kg of polyethylene wax is specifically selected.
In this preparation example, the preparation method of the MDOPE substrate layer comprises the following steps:
uniformly mixing linear low-density polyethylene, chlorosulfonated polyethylene A, chlorosulfonated polyethylene B, a heat stabilizer and a lubricant, and then performing melt extrusion in an extruder, wherein the temperature of the extruder is set to 160-170 ℃ and the temperature of a die head is set to 170-180 ℃; and then cooling and longitudinally stretching after film blowing to form a film bubble to obtain the MDOPE substrate layer, wherein the temperature during longitudinal stretching is controlled to be 90-100 ℃, and the stretching ratio is controlled to be 2:1.
Preparation example 4
An MDOPE substrate layer comprises the following raw materials in parts by weight:
linear low density polyethylene: 70kg, melt index 3.8g/10min;
chlorosulfonated polyethylene a:10kg, a melt index of 1.0g/10min and a chlorine content of 15%;
chlorosulfonated polyethylene B:20kg, melt index of 2.8g/10min and chlorine content of 36%;
heat stabilizer: 3kg of calcium stearate is specifically selected;
and (3) a lubricant: 0.5kg of polyethylene wax is specifically selected.
In this preparation example, the preparation method of the MDOPE substrate layer comprises the following steps:
uniformly mixing linear low-density polyethylene, chlorosulfonated polyethylene A, chlorosulfonated polyethylene B, a heat stabilizer and a lubricant, and then performing melt extrusion in an extruder, wherein the temperature of the extruder is set to 160-170 ℃ and the temperature of a die head is set to 170-180 ℃; and then cooling and longitudinally stretching after film blowing to form a film bubble to obtain the MDOPE substrate layer, wherein the temperature during longitudinal stretching is controlled to be 90-100 ℃, and the stretching ratio is controlled to be 2:1.
PE inner layer preparation example
Preparation example A
A PE inner layer comprising 35kg metallocene polyethylene a, 15kg metallocene polyethylene B and 100kg low density polyethylene.
Wherein the melt index of the metallocene polyethylene A is 0.8g/10min;
the melt index of the metallocene polyethylene B is 6.8g/10min;
the melt index of the low density polyethylene was 1g/10min.
In this preparation example, the preparation method of the PE inner layer includes the following steps:
uniformly mixing metallocene polyethylene A, metallocene polyethylene B and low-density polyethylene, and then putting the mixture into an extruder for melt extrusion, wherein the temperature of the extruder is set to be 190-210 ℃ and the die head temperature is set to be 210-220 ℃; and then cooling and biaxially stretching after film blowing to form film bubble, so as to obtain the PE inner layer, wherein the temperature is controlled at 100-110 ℃ during longitudinal stretching, the stretching ratio is controlled at 1.5:1, and the temperature is controlled at 115-125 ℃ during transverse stretching, and the stretching ratio is controlled at 1.2:1.
Preparation example B
A PE inner layer comprising 35kg metallocene polyethylene a, 15kg metallocene polyethylene B and 100kg low density polyethylene.
Wherein the melt index of the metallocene polyethylene A is 1.5g/10min;
the melt index of the metallocene polyethylene B is 4.2g/10min;
the melt index of the low density polyethylene was 2g/10min.
In this preparation example, the preparation method of the PE inner layer includes the following steps:
uniformly mixing metallocene polyethylene A, metallocene polyethylene B and low-density polyethylene, and then putting the mixture into an extruder for melt extrusion, wherein the temperature of the extruder is set to be 190-210 ℃ and the die head temperature is set to be 210-220 ℃; and then cooling and biaxially stretching after film blowing to form film bubble, so as to obtain the PE inner layer, wherein the temperature is controlled at 100-110 ℃ during longitudinal stretching, the stretching ratio is controlled at 1.5:1, and the temperature is controlled at 115-125 ℃ during transverse stretching, and the stretching ratio is controlled at 1.2:1.
Preparation example C
A PE inner layer comprising 35kg metallocene polyethylene a, 15kg metallocene polyethylene B and 100kg low density polyethylene.
Wherein the melt index of the metallocene polyethylene A is 1.2g/10min;
the melt index of the metallocene polyethylene B is 5.8g/10min;
the melt index of the low density polyethylene was 2g/10min.
In this preparation example, the preparation method of the PE inner layer includes the following steps:
uniformly mixing metallocene polyethylene A, metallocene polyethylene B and low-density polyethylene, and then putting the mixture into an extruder for melt extrusion, wherein the temperature of the extruder is set to be 190-210 ℃ and the die head temperature is set to be 210-220 ℃; and then cooling and biaxially stretching after film blowing to form film bubble, so as to obtain the PE inner layer, wherein the temperature is controlled at 100-110 ℃ during longitudinal stretching, the stretching ratio is controlled at 1.5:1, and the temperature is controlled at 115-125 ℃ during transverse stretching, and the stretching ratio is controlled at 1.2:1.
Preparation example D
A PE inner layer comprising 35kg metallocene polyethylene a, 15kg metallocene polyethylene B and 100kg low density polyethylene.
Wherein the melt index of the metallocene polyethylene A is 1.2g/10min;
the melt index of the metallocene polyethylene B is 6.8g/10min;
the melt index of the low density polyethylene was 2g/10min.
In this preparation example, the preparation method of the PE inner layer includes the following steps:
uniformly mixing metallocene polyethylene A, metallocene polyethylene B and low-density polyethylene, and then putting the mixture into an extruder for melt extrusion, wherein the temperature of the extruder is set to be 190-210 ℃ and the die head temperature is set to be 210-220 ℃; and then cooling and biaxially stretching after film blowing to form film bubble, so as to obtain the PE inner layer, wherein the temperature is controlled at 100-110 ℃ during longitudinal stretching, the stretching ratio is controlled at 1.5:1, and the temperature is controlled at 115-125 ℃ during transverse stretching, and the stretching ratio is controlled at 1.2:1.
Preparation example E
A PE inner layer comprising 35kg metallocene polyethylene a, 15kg metallocene polyethylene B and 100kg low density polyethylene.
Wherein the melt index of the metallocene polyethylene A is 4.2g/10min;
the melt index of the metallocene polyethylene B is 8.8g/10min;
the melt index of the low density polyethylene was 2g/10min.
In this preparation example, the preparation method of the PE inner layer includes the following steps:
uniformly mixing metallocene polyethylene A, metallocene polyethylene B and low-density polyethylene, and then putting the mixture into an extruder for melt extrusion, wherein the temperature of the extruder is set to be 190-210 ℃ and the die head temperature is set to be 210-220 ℃; and then cooling and biaxially stretching after film blowing to form film bubble, so as to obtain the PE inner layer, wherein the temperature is controlled at 100-110 ℃ during longitudinal stretching, the stretching ratio is controlled at 1.5:1, and the temperature is controlled at 115-125 ℃ during transverse stretching, and the stretching ratio is controlled at 1.2:1.
Examples
Example 1
Referring to fig. 1, a composite aluminizer comprises an MDOPE substrate layer 1, a PVA adhesive layer 2, an alumina layer 3 and a PE inner layer 4 which are sequentially arranged; wherein the MDOPE substrate layer 1 is the MDOPE substrate layer 1 prepared in preparation example 1, the thickness is 25 μm, the thickness of the PVA adhesive layer 2 is 1.5 μm, the thickness of the alumina layer 3 is 400 angstrom, the PE inner layer 4 is the PE inner layer 4 prepared in preparation example A, and the thickness of the PE inner layer 4 is 45 μm.
In this embodiment, the preparation method of the composite aluminizer includes the following steps:
feeding the PE inner layer 4 into vacuum aluminizing equipment, heating an aluminum wire, introducing oxygen in the aluminum evaporation process, enabling the oxygen to react with gaseous aluminum to generate aluminum oxide, and depositing on one side of the PE inner layer 4 through the action of physical vapor deposition to obtain an aluminum oxide layer 3, thereby obtaining a composite aluminum oxide film; wherein the diameter of the aluminum wire is 1.8mm, the wire feeding speed of the aluminum wire is 250mm/min, and the flow rate of oxygen is 15000sccm;
and coating a PVA adhesive layer 2 on one side of the MDOPE substrate layer 1, and then immediately compounding the aluminum oxide layer 3 of the composite aluminum oxide film with the PVA adhesive layer 2, and drying to obtain the composite aluminum-plated film.
Example 2
Referring to fig. 1, a composite aluminizer comprises an MDOPE substrate layer 1, a PVA adhesive layer 2, an alumina layer 3 and a PE inner layer 4 which are sequentially arranged; wherein the MDOPE substrate layer 1 was the MDOPE substrate layer 1 prepared in preparation example 2, the thickness was 25 μm, the thickness of the PVA adhesive layer 2 was 1.5 μm, the thickness of the alumina layer 3 was 400 angstroms, the PE inner layer 4 was the PE inner layer 4 prepared in preparation example A, and the thickness of the PE inner layer 4 was 45 μm.
In this example, the preparation method of the composite aluminizer was the same as that in example 1.
Example 3
Referring to fig. 1, a composite aluminizer comprises an MDOPE substrate layer 1, a PVA adhesive layer 2, an alumina layer 3 and a PE inner layer 4 which are sequentially arranged; wherein the MDOPE substrate layer 1 was the MDOPE substrate layer 1 prepared in preparation example 3, the thickness was 25 μm, the thickness of the PVA adhesive layer 2 was 1.5 μm, the thickness of the alumina layer 3 was 400 angstroms, the PE inner layer 4 was the PE inner layer 4 prepared in preparation example A, and the thickness of the PE inner layer 4 was 45 μm.
In this example, the preparation method of the composite aluminizer was the same as that in example 1.
Example 4
Referring to fig. 1, a composite aluminizer comprises an MDOPE substrate layer 1, a PVA adhesive layer 2, an alumina layer 3 and a PE inner layer 4 which are sequentially arranged; wherein the MDOPE substrate layer 1 was the MDOPE substrate layer 1 prepared in preparation example 4, the thickness was 25 μm, the thickness of the PVA adhesive layer 2 was 1.5 μm, the thickness of the alumina layer 3 was 400 angstroms, the PE inner layer 4 was the PE inner layer 4 prepared in preparation example A, and the thickness of the PE inner layer 4 was 45 μm.
In this example, the preparation method of the composite aluminizer was the same as that in example 1.
Example 5
Referring to fig. 1, a composite aluminizer comprises an MDOPE substrate layer 1, a PVA adhesive layer 2, an alumina layer 3 and a PE inner layer 4 which are sequentially arranged; wherein the MDOPE substrate layer 1 was the MDOPE substrate layer 1 prepared in preparation example 4, the thickness was 25 μm, the thickness of the PVA adhesive layer 2 was 1.5 μm, the thickness of the alumina layer 3 was 400 angstroms, the PE inner layer 4 was the PE inner layer 4 prepared in preparation example B, and the thickness of the PE inner layer 4 was 45 μm.
In this example, the preparation method of the composite aluminizer was the same as that in example 1.
Example 6
Referring to fig. 1, a composite aluminizer comprises an MDOPE substrate layer 1, a PVA adhesive layer 2, an alumina layer 3 and a PE inner layer 4 which are sequentially arranged; wherein the MDOPE base material layer 1 was the MDOPE base material layer 1 prepared in preparation example 4, the thickness was 25 μm, the thickness of the PVA adhesive layer 2 was 1.5 μm, the thickness of the alumina layer 3 was 400 angstroms, the PE inner layer 4 was the PE inner layer 4 prepared in preparation example C, and the thickness of the PE inner layer 4 was 45 μm.
In this example, the preparation method of the composite aluminizer was the same as that in example 1.
Example 7
Referring to fig. 1, a composite aluminizer comprises an MDOPE substrate layer 1, a PVA adhesive layer 2, an alumina layer 3 and a PE inner layer 4 which are sequentially arranged; wherein the MDOPE base material layer 1 was the MDOPE base material layer 1 prepared in preparation example 4, the thickness was 25 μm, the thickness of the PVA adhesive layer 2 was 1.5 μm, the thickness of the alumina layer 3 was 400 angstroms, the PE inner layer 4 was the PE inner layer 4 prepared in preparation example D, and the thickness of the PE inner layer 4 was 45 μm.
In this example, the preparation method of the composite aluminizer was the same as that in example 1.
Example 8
Referring to fig. 1, a composite aluminizer comprises an MDOPE substrate layer 1, a PVA adhesive layer 2, an alumina layer 3 and a PE inner layer 4 which are sequentially arranged; wherein the MDOPE base material layer 1 is the MDOPE base material layer 1 prepared in preparation example 4, the thickness is 25 μm, the thickness of the PVA adhesive layer 2 is 1.5 μm, the thickness of the alumina layer 3 is 400 angstrom, the PE inner layer 4 is the PE inner layer 4 prepared in preparation example E, and the thickness of the PE inner layer 4 is 45 μm.
In this example, the preparation method of the composite aluminizer was the same as that in example 1.
Comparative example
Comparative example 1
The difference from example 1 is that: the MDOPE substrate layer 1 has a different composition of raw materials. In this comparative example: the MDOPE substrate layer 1 comprises the following raw materials in parts by weight:
linear low density polyethylene: 70kg, melt index 3.8g/10min;
chlorosulfonated polyethylene a:30kg, a melt index of 0.3g/10min and a chlorine content of 10%;
heat stabilizer: 3kg of calcium stearate is specifically selected;
and (3) a lubricant: 0.5kg of polyethylene wax is specifically selected.
The preparation method of the MDOPE substrate layer 1 is as follows:
uniformly mixing linear low-density polyethylene, chlorosulfonated polyethylene A, a heat stabilizer and a lubricant, and then performing melt extrusion in an extruder, wherein the temperature of the extruder is set to 160-170 ℃ and the temperature of a die head is set to 170-180 ℃; and then cooling and longitudinally stretching after film blowing to form a film bubble to obtain the MDOPE substrate layer 1, wherein the temperature during longitudinal stretching is controlled to be 90-100 ℃, and the stretching ratio is controlled to be 2:1.
Comparative example 2
The difference from example 1 is that: the MDOPE substrate layer 1 has a different composition of raw materials. In this comparative example: the MDOPE substrate layer 1 comprises the following raw materials in parts by weight:
linear low density polyethylene: 70kg, melt index 3.8g/10min;
chlorosulfonated polyethylene B:30kg, a melt index of 3g/10min and a chlorine content of 37%;
heat stabilizer: 3kg of calcium stearate is specifically selected;
and (3) a lubricant: 0.5kg of polyethylene wax is specifically selected.
The preparation method of the MDOPE substrate layer 1 is as follows:
uniformly mixing linear low-density polyethylene, chlorosulfonated polyethylene B, a heat stabilizer and a lubricant, and then performing melt extrusion in an extruder, wherein the temperature of the extruder is set to 160-170 ℃ and the temperature of a die head is set to 170-180 ℃; and then cooling and longitudinally stretching after film blowing to form a film bubble to obtain the MDOPE substrate layer 1, wherein the temperature during longitudinal stretching is controlled to be 90-100 ℃, and the stretching ratio is controlled to be 2:1.
Comparative example 3
The difference from example 1 is that: the MDOPE substrate layer 1 has a different composition of raw materials. In this comparative example: the MDOPE substrate layer 1 comprises the following raw materials in parts by weight:
linear low density polyethylene: 70kg, melt index 3.8g/10min;
chlorosulfonated polyethylene C:10kg, melt index of 2.9g/10min, chlorine content of 37%;
chlorosulfonated polyethylene D:20kg, a melt index of 4.8g/10min and a chlorine content of 42%;
heat stabilizer: 3kg of calcium stearate is specifically selected;
and (3) a lubricant: 0.5kg of polyethylene wax is specifically selected.
The preparation method of the MDOPE substrate layer 1 is as follows:
uniformly mixing linear low-density polyethylene, chlorosulfonated polyethylene C, chlorosulfonated polyethylene D, a heat stabilizer and a lubricant, and then performing melt extrusion in an extruder, wherein the temperature of the extruder is set to 160-170 ℃ and the temperature of a die head is set to 170-180 ℃; and then cooling and longitudinally stretching after film blowing to form a film bubble to obtain the MDOPE substrate layer 1, wherein the temperature during longitudinal stretching is controlled to be 90-100 ℃, and the stretching ratio is controlled to be 2:1.
Comparative example 4
The difference from example 1 is that: the MDOPE substrate layer 1 has a different composition of raw materials. In this comparative example: the MDOPE substrate layer 1 comprises the following raw materials in parts by weight:
linear low density polyethylene: 100kg, comprising 70kg of linear low density polyethylene with a melt index of 3.8g/10min, 10kg of linear low density polyethylene with a melt index of 0.3g/10min, and 20kg of linear low density polyethylene with a melt index of 3g/10min; heat stabilizer: 3kg of calcium stearate is specifically selected;
and (3) a lubricant: 0.5kg of polyethylene wax is specifically selected.
In this preparation example, the preparation method of the MDOPE base material layer 1 is as follows:
uniformly mixing linear low-density polyethylene, a heat stabilizer and a lubricant, and then carrying out melt extrusion in an extruder, wherein the temperature of the extruder is set to 160-170 ℃ and the temperature of a die head is set to 170-180 ℃; and then cooling and longitudinally stretching after film blowing to form a film bubble to obtain the MDOPE substrate layer 1, wherein the temperature during longitudinal stretching is controlled to be 90-100 ℃, and the stretching ratio is controlled to be 2:1.
Comparative example 5
A composite aluminizer, differing from comparative example 4 in that:
the MDOPE substrate layer 1 is corona treated prior to coating the PVA adhesive layer 2.
Performance detection parameters
1. Surface quality: the surface of the composite aluminized film in each of examples and comparative examples was visually inspected for localized white spots and recorded in table 1 below.
2. Printing performance: the inks with the same area size were printed on the MDOPE base material layers of the composite aluminized films in each example and comparative example, respectively, after the inks were dried, the adhesive tape was stuck on the ink position, the adhesive tape was flattened by hand to be closely attached to the MDOPE base material layer, then the adhesive tape was slowly lifted up, the sticking condition of the ink by the adhesive tape was observed, and the average peeled area of the ink was recorded in table 1 below.
3. Attachment fastness: the composite aluminized films in each example and comparative example were put into water, heated to 80 ℃, boiled in water for 30min, taken out for cooling, and observed for delamination, and recorded in table 1 below.
4. Heat seal strength: the composite aluminized films prepared in each example and comparative example were bagged by a heat-sealing process under the following conditions at 100℃under a pressure of 0.3MPa for a heat-sealing time of 1s. The heat seal strength was tested.
5. Dimensional stability: respectively putting a weight with the weight of 1kg into the bags prepared by compounding aluminized films in each example and comparative example, standing for 12 hours in a state of being vertical and not contacting other carriers, wherein the initial length of the bags is 20cm, the initial width of the bags is 12cm, and recording the length change rate of the bags corresponding to each example and comparative example after bearing.
6. Oxygen transmission rate test: the oxygen transmission rates of the composite aluminized films in the examples and comparative examples were tested according to ASTM D3985, wherein a smaller oxygen transmission rate indicates a better oxygen barrier performance. The oxidation transmittance of the application is less than or equal to 0.3 cc/square meter.
7. Water vapor transmission rate test: the water vapor transmission rate of the composite aluminized film in each of the examples and comparative examples was tested according to ASTM F1249, wherein a smaller water vapor transmission rate indicates a better water vapor barrier performance. The water vapor transmittance of the application is less than or equal to 0.3 g/square meter.
TABLE 1
Combining example 1 with comparative examples 1-4 and combining the data in table 1, it is seen that chlorosulfonated polyethylene a, chlorosulfonated polyethylene B, and linear low density polyethylene within a specific melt index range have a synergistic effect, and can improve the bonding force between the MDOPE substrate layer and the PVA adhesive layer and the dimensional stability of the composite aluminized film while improving the printing performance of the MDOPE substrate layer.
As can be seen from the data in table 1 in combination with examples 1 and comparative examples 4 to 5, the MDOPE base material layer used in the composite aluminized film of the present application can obtain excellent printing performance without corona treatment, and the surface does not generate local white spots, and the stability between the materials of each layer is strong.
When the melt indexes of chlorosulfonated polyethylene A and chlorosulfonated polyethylene B are 1.5-1.8g/10min, the adhesion fastness between the MDOPE substrate layer and the PVA adhesive layer can be effectively improved, and the dimensional stability of the composite aluminized film can be further improved as shown by combining the data in the examples 1 and 3-4 and combining the data in the table 1.
It is known from the data in Table 1 in combination with examples 4 to 8 that when the melt indexes of the metallocene polyethylene A and the metallocene polyethylene B are within a specific range and differ by 4.5 to 5g/10min, the oxygen resistance and the water vapor resistance of the composite aluminized film are improved, and meanwhile, the dimensional stability of the composite aluminized film is also improved.
The present embodiment is merely illustrative of the present application and not limiting, and one skilled in the art, after having read the present specification, may make modifications to the embodiment without creative contribution as required, but is protected by patent law within the scope of the claims of the present application.

Claims (9)

1. The utility model provides a compound aluminizer which characterized in that: comprises an MDOPE substrate layer (1), a PVA adhesive layer (2), an alumina layer (3) and a PE inner layer (4) which are sequentially arranged; the MDOPE substrate layer (1) is obtained by carrying out melt blending on a main material and an auxiliary agent, and then carrying out extrusion and unidirectional stretching;
the main materials comprise linear low density polyethylene, chlorosulfonated polyethylene A and chlorosulfonated polyethylene B, wherein the weight ratio of the linear low density polyethylene to the chlorosulfonated polyethylene A to the chlorosulfonated polyethylene B is (60-70): (10-20), wherein the linear low density polyethylene has a melt index in the range of 2.8-6.4g/10min, the chlorosulfonated polyethylene A has a melt index in the range of 0.3-1.2g/10min, and the chlorosulfonated polyethylene B has a melt index in the range of 2-3g/10min;
the auxiliary agent is selected from any one or a combination of a plurality of antioxidants, heat stabilizers and lubricants;
the melt index of the chlorosulfonated polyethylene A and the melt index of the chlorosulfonated polyethylene B are 1.5-1.8g/10min.
2. A composite aluminizer according to claim 1, characterized in that: the linear low density polyethylene has a melt index in the range of 3.8-4.6g/10min.
3. A composite aluminizer according to claim 1, characterized in that: the PE inner layer (4) comprises a metallocene polyethylene A, a metallocene polyethylene B and low-density polyethylene, wherein the weight ratio of the metallocene polyethylene A to the metallocene polyethylene B to the low-density polyethylene is (3-4): (1-2): 10, the melt index range of the metallocene polyethylene A is 0.8-1.5g/10min, the melt index range of the metallocene polyethylene B is 4.2-6.8g/10min, and the melt index range of the low-density polyethylene is 1-2g/10min.
4. A composite aluminizer according to claim 3, characterized in that: the melt index of the metallocene polyethylene A and the melt index of the metallocene polyethylene B are 4.5-5g/10min.
5. A composite aluminizer according to claim 1, characterized in that: the MDOPE substrate layer (1) has a thickness of 18-25 μm.
6. A composite aluminizer according to claim 1, characterized in that: the thickness of the PVA adhesive layer (2) is 1-2 mu m.
7. A composite aluminizer according to claim 1, characterized in that: the thickness of the alumina layer (3) is 300-500 angstrom.
8. A composite aluminizer according to claim 1, characterized in that: the thickness of the PE inner layer (4) is 40-60 mu m.
9. A method for producing a composite aluminized film according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
feeding the PE inner layer (4) into vacuum aluminizing equipment, heating an aluminum wire, introducing oxygen in the aluminum evaporation process, enabling the oxygen to react with gaseous aluminum to generate aluminum oxide, and depositing on one side of the PE inner layer (4) through physical vapor deposition to obtain an aluminum oxide layer (3) to obtain a composite aluminum oxide film;
and coating a PVA adhesive layer (2) on one side of the MDOPE substrate layer (1), and then immediately compounding the aluminum oxide layer (3) of the composite aluminum oxide film with the PVA adhesive layer (2) and drying to obtain the composite aluminum-plated film.
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GB847164A (en) * 1957-06-19 1960-09-07 Du Pont Synthetic elastomers
US4098739A (en) * 1976-03-26 1978-07-04 The British Petroleum Company Limited Blends containing modified polyethylene
CN101891034A (en) * 2004-05-17 2010-11-24 胡赫塔迈基德国有限及两合公司胡赫塔迈基龙斯贝格分公司 Have the best and tear the stand-up pouch and the manufacture method thereof of characteristic
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