CN112757730B - PETG multilayer composite film for packaging and preparation method thereof - Google Patents

PETG multilayer composite film for packaging and preparation method thereof Download PDF

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CN112757730B
CN112757730B CN202110161046.1A CN202110161046A CN112757730B CN 112757730 B CN112757730 B CN 112757730B CN 202110161046 A CN202110161046 A CN 202110161046A CN 112757730 B CN112757730 B CN 112757730B
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petg
packaging
multilayer composite
composite film
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CN112757730A (en
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张启纲
李沅鸿
王威威
蔡文彬
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Henan Yinjinda New Materials Co ltd
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Henan Yinjinda New 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
    • B32B27/06—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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 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
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2231—Oxides; Hydroxides of metals of tin
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • 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 belongs to the field of packaging materials, and particularly relates to a PETG multilayer composite film for packaging and a preparation method thereof. The invention provides a PETG multilayer composite film for packaging, which comprises an ABC three-layer film layer, wherein a layer A is a heat sealing layer, a layer B is a barrier layer, a layer C is a supporting layer, the component of the layer A is PETG, and the layer B consists of the following components in percentage by mass: 29-39.5% of PHA, 60-70% of PETG and 0.5-1% of nano tin dioxide, wherein the C layer consists of the following components in percentage by mass: 70-80% of PLA and 20-30% of PETG; the PETG multilayer composite film for packaging has good barrier property, high tensile strength and high elongation at break, and is environment-friendly.

Description

PETG multilayer composite film for packaging and preparation method thereof
Technical Field
The invention belongs to the field of packaging materials, and particularly relates to a PETG multilayer composite film for packaging and a preparation method thereof.
Background
Food packaging materials are materials used for manufacturing packaging containers, packaging decoration, packaging printing, packaging transportation, and the like, which meet the packaging requirements of products. At present, materials commonly used for food packaging comprise plastics, glass, metals, wood, paper and the like, wherein the plastic packaging material has the advantages of low specific gravity, light weight, easy processing, abundant resources, low energy consumption, low cost, protection effect on food and the like due to the characteristics of good plasticity, elasticity, insulativity, chemical inertness and the like. The plastic packaging material gradually replaces the traditional packaging materials such as paper, glass and the like, and is one of the most main packaging materials in food packaging. At present, plastic materials for food packaging in China mainly comprise Polyethylene (PE), polypropylene (PP), polyester (PET), polyvinylidene chloride (PVDC), polycarbonate (PC), polystyrene (PS), polyamide (PA), polyvinyl alcohol (PVA) and the like, but the plastic packaging materials also have certain defects and shortcomings: (1) the stability is poor, the high temperature resistance and the easy deformation are not realized; (2) plastic raw materials and processing aids may contaminate packaged foods, affecting human health, for example: a plasticizer; (3) the petroleum-based plastics are difficult to bring white pollution due to mass use and degradation, and have great influence on the environment.
With the increasing severity of environmental pollution, low carbon, energy conservation and environmental protection have become the focus of global attention, and therefore, green packaging has received more and more attention and popularization. The green packaging material is a packaging material which does not harm natural environment and human health in the whole life cycle, can be recycled at the later stage or can be automatically degraded without polluting the environment, and can effectively reduce the consumption of non-renewable resources. The degradability of plastic packaging materials is a hot spot and difficulty in future packaging materials.
Currently under development are starch-based degradable materials, polylactic acid degradable plastics, water-soluble plastic films and the like. The materials are more prepared by adding a small amount of degradable materials into traditional plastics such as PP, PE and the like to achieve the purposes of reducing cost and increasing the degradability of the plastics, but the problem of incomplete degradation is solved, and some resin molecular frameworks are difficult to degrade for a long time and remain in the natural environment in the form of fragments or powder, so that the difficulty of recycling waste plastics is aggravated. In addition, as the degradable plastic is a high polymer material prepared by taking natural degradable substances such as polysaccharide, protein and the like as raw materials, the mechanical strength and toughness of the degradable plastic are slightly inferior to those of petroleum-based plastics (such as starch-based degradable plastics have the defects of high brittleness and easy breakage), even the degradable plastic has the problem of failure in the use process, and the degradation controllability is poor, so that the application range of the degradable plastic can be influenced.
In recent years, regarding research on food packaging materials, the focus at home and abroad is mainly on developing functional and environment-friendly green food packaging materials, and improving the functionality, safety and environment-friendliness of the food packaging materials is a requirement of sustainable development strategy in China, and it is necessary to provide functional, safety and environment-friendly food packaging materials.
Disclosure of Invention
In order to overcome the defects and the shortcomings of the prior art, the primary aim of the invention is to provide a PETG multilayer composite film for packaging.
The invention also aims to provide a preparation method of the PETG multilayer composite film for packaging.
It is still another object of the present invention to provide the use of the above-mentioned PETG multilayer composite film for packaging.
The aim of the invention is achieved by the following technical scheme:
the PETG multilayer composite film for packaging comprises an ABC three-layer film layer, wherein the A layer is a heat sealing layer, the B layer is a barrier layer, the C layer is a supporting layer, the A layer comprises PETG, and the B layer comprises the following components in percentage by mass: 29-39.5% of PHA, 60-70% of PETG and 0.5-1% of nano tin dioxide, wherein the C layer consists of the following components in percentage by mass: 70-80% of PLA and 20-30% of PETG;
the PETG in the layer A is preferably SKYGREEN (S2008), GN071 (Izeman in the United states) or 0603 (Izeman in the United states);
the PETG of the B layer and the C layer is preferably at least one of K2012 (Korean SK), KN200 (Korean SK) and EB062 (Izeman in the United states), and the PETG has high viscosity and good barrier property;
the PHA is preferably P34HB, 4HB is introduced into the PHA, the crystallization regularity is damaged, the crystallinity is reduced, the fluidity of a macromolecular chain is greatly improved, the crystallization rate is improved, the hardness is reduced, the ductility is improved, and the mechanical property and the thermal stability are improved;
the PLA is preferably at least one of 2003D (Nature Works) and 2500HP (Nature Works);
the preparation method of the PETG multilayer composite film for packaging comprises the following steps:
(1) Respectively mixing the raw materials of each layer of the PETG multilayer composite film for packaging, and then carrying out melting plasticization in different extruders; then feeding the molten steel into a three-layer co-extrusion circular die head for melt molding to obtain a circular melt tube blank;
(2) The circular melt tube blank is subjected to vacuum sizing, cooling and molding, then is preheated in a hot water tank, and then is transversely blown up and longitudinally stretched;
(3) Carrying out irradiation treatment and heat treatment on the film after blow molding, and finally rolling to obtain a PETG multilayer composite film for packaging;
the temperature of the three-layer co-extrusion circular die head in the step (1) is preferably 180-185 ℃;
the transverse inflation in the step (2) has an inflation ratio of 2.5-3.0;
the stretching ratio of the longitudinal stretching in the step (2) is 2.5-3.0;
the radiation dose of the irradiation treatment in the step (3) is preferably 100-300 kGy;
the heat treatment condition in the step (3) is preferably 80-90 ℃ for 5-20 min;
the PETG multilayer composite film for packaging is prepared by the preparation method;
the PETG multilayer composite film for packaging is applied to packaging materials;
compared with the prior art, the invention has the following advantages and effects:
(1) The invention provides a PETG multilayer composite film for packaging, which comprises an ABC three-layer film layer (figure 1), wherein a layer A is a heat seal layer, a layer B is a barrier layer, a layer C is a supporting layer and an adhesive layer is not needed, wherein the heat seal layer consists of PETG with good heat seal strength and proper heat seal temperature, the barrier layer consists of PETG with good gas barrier effect and PHA, the supporting layer consists of PLA and PETG, the three-layer structure comprises PETG, the content of the PETG is reduced layer by layer, the compatibility among polymers is improved through PETG with different contents, the film layers are not easy to slide and peel, and the three-layer film layers are all green environment-friendly materials;
(2) The P34HB type PHA selected by the invention introduces 4HB, so that the crystallization regularity is damaged, the crystallinity is reduced, the mobility of a macromolecular chain is greatly improved, the crystallization rate is favorably improved, the ductility is further improved, and the mechanical property and the thermal stability are improved;
(3) According to the invention, nano tin dioxide is added between functional layers, wherein the nano material improves the antistatic capability of the film, and on one hand, the existence of metallic tin element reduces the formation of large-size spherulites in the process of melt extrusion of PHA, improves the crystallization rate, and further improves the toughness and ductility of PHA;
(4) The invention can avoid the secondary crystallization phenomenon and the formation of spherulites of PHA in the room temperature process by the form of irradiation and heat treatment;
(5) According to the invention, the PETG with low crystallinity is added into the PLA and the PHA, so that the problems of large brittleness, poor stability, low crystallization speed and the like of the PLA and the PHA can be effectively solved;
(6) The PETG multilayer composite film for packaging provided by the invention has good barrier property and higher tensile strength and elongation at break.
Drawings
Fig. 1 is a schematic structural view of a PETG multilayer composite film for packaging provided by the invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
(1) PLA (2003D), P34HB (shenzhen keman), PETG SKYGREEN S2008 and EB062 are dried and dehumidified before melt extrusion, for later use:
(2) The packaging PETG multilayer composite film is prepared by respectively mixing the raw materials of all layers, wherein the component of an A layer (heat sealing layer) is PETG (PETGSKYGREEN body S2008), and a B layer (barrier layer) consists of the following components in percentage by mass: 34.2% of P34HB and 65% of PETG (EB 062) and 0.8% of nano tin dioxide, and the layer C (supporting layer) consists of the following components in percentage by mass: 75% PLA (2003D) and 25% PETG (EB 062); after the materials are prepared, each layer is melted and plasticized in different extruders; then feeding the molten steel into a three-layer co-extrusion circular die head with the temperature of 180 ℃ for melt molding to obtain a circular melt tube blank;
(3) Preheating the circular melt tube blank in a hot water tank after vacuum sizing and cooling forming, and flushing compressed air after preheating to carry out transverse inflation and longitudinal stretching, wherein the inflation ratio is 2.8, and the stretching ratio is 2.5;
(4) Carrying out irradiation treatment on the film subjected to blow molding by adopting an electron accelerator, wherein the radiation dose is 200 kGy; and then carrying out heat treatment at 85 ℃ for 10min, and then rolling to obtain the PETG multilayer composite film for packaging, wherein the thickness ratio of the layer A to the layer B to the layer C is 40:15:45.
example 2
(1) PLA (2003D), P34HB (shenzhen keman), PETGSKYGREEN S2008 and EB062 are dried and dehumidified before melt extrusion, for later use:
(2) The packaging PETG multilayer composite film is prepared by respectively mixing the raw materials of all layers, wherein the component of an A layer (heat sealing layer) is PETG (PETGSKYGREEN body S2008), and a B layer (barrier layer) consists of the following components in percentage by mass: 29% of P34HB, 70% of PETG (EB 062) and 1% of nano tin dioxide, and a C layer (supporting layer) consists of the following components in percentage by mass: 70% PLA (2003D) and 30% PETG (EB 062); after the materials are prepared, each layer is melted and plasticized in different extruders; then feeding the molten steel into a three-layer co-extrusion circular die head with the temperature of 180 ℃ for melt molding to obtain a circular melt tube blank;
(3) Preheating the circular melt tube blank in a hot water tank after vacuum sizing and cooling forming, and flushing compressed air after preheating to carry out transverse inflation and longitudinal stretching, wherein the inflation ratio is 3.0, and the stretching ratio is 2.5;
(4) Carrying out irradiation treatment on the film subjected to blow molding by adopting an electron accelerator, wherein the radiation dose is 120 kGy; and then carrying out heat treatment at 80 ℃ for 15min, and then rolling to obtain the PETG multilayer composite film for packaging, wherein the thickness ratio of the layer A to the layer B to the layer C is 45:13:42.
example 3
(1) PLA (2003D), P34HB (shenzhen keman), PETGSKYGREEN S2008 and EB062 are dried and dehumidified before melt extrusion, for later use:
(2) The packaging PETG multilayer composite film is prepared by respectively mixing the raw materials of all layers, wherein the component of an A layer (heat sealing layer) is PETG (PETGSKYGREEN body S2008), and a B layer (barrier layer) consists of the following components in percentage by mass: 39.5% of P34HB and 60% of PETG (EB 062) and 0.5% of nano tin dioxide, and the layer C (supporting layer) consists of the following components in percentage by mass: 80% PLA (2003D) and 20% PETG (EB 062); after the materials are prepared, each layer is melted and plasticized in different extruders; then feeding the mixture into a three-layer co-extrusion circular die head with the temperature of 185 ℃ for melt molding to obtain a circular melt tube blank;
(3) Preheating the circular melt tube blank in a hot water tank after vacuum sizing and cooling forming, and flushing compressed air after preheating to carry out transverse inflation and longitudinal stretching, wherein the inflation ratio is 2.5, and the stretching ratio is 2.5;
(4) Carrying out irradiation treatment on the film subjected to blow molding by adopting an electron accelerator, wherein the radiation dose is 150 kGy; and then carrying out heat treatment at 90 ℃ for 5min, and then rolling to obtain the PETG multilayer composite film for packaging, wherein the thickness ratio of the layer A to the layer B to the layer C is 40:20:40.
comparative example 1
In this example, layer C (support layer) was prepared from PLA (2003D) and the other layers were prepared in the same manner as in example 1.
Comparative example 2
The layer B (barrier layer) in this example consists of the following components in mass percent: 40% P34HB and 60% PETG (EB 062), the other layers were made in the same manner as in example 1.
The thickness, tensile strength, elongation at break, heat-sealing temperature, heat-sealing strength, water vapor transmission amount, oxygen transmission amount, and the like of the PETG multilayer composite films for packaging produced in examples 1 to 3 and comparative examples 1 to 2 were respectively examined. Wherein, the tensile strength and elongation at break are carried out according to the GB/T1040.3 method, the heat sealing performance is carried out according to the BMSTT01 method, and the oxygen permeability and the like are carried out according to ASRM related methods.
The results are shown in Table 1.
Table 1 Properties of PETG multilayer composite films for packaging produced in examples 1 to 3 and comparative examples 1 to 2
Figure DEST_PATH_IMAGE001
As can be seen from table 1, the multilayer composite film of PETG for packaging (comparative example 1) prepared from 100% PLA (2003D) for layer C (support layer) is lower in tensile strength and elongation at break than the multilayer composite film of PETG for packaging prepared in examples 1 to 3, indicating that the addition of PETG in layer C (support layer) can effectively improve the toughness and ductility of the film, while also affecting the barrier properties of the film; however, the addition of tin dioxide can reduce the formation of large-sized spherulites in PHA, and thus increase the crystallization rate, and further increase the tensile strength and elongation at break, as can be seen from Table 1, the multilayer composite film prepared in comparative example 2 is significantly lower in tensile strength and elongation at break than the packaging PETG multilayer composite films prepared in examples 1-3.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (5)

1. The PETG multilayer composite film for packaging is characterized by comprising an ABC three-layer film layer, wherein the A layer is a heat seal layer, the B layer is a barrier layer, the C layer is a support layer, the component of the A layer is PETG, and the B layer consists of the following components in percentage by mass: 29-39.5% of PHA, 60-70% of PETG and 0.5-1% of nano tin dioxide, wherein the C layer consists of the following components in percentage by mass: 70-80% of PLA and 20-30% of PETG;
the PHA is P34HB;
the PETG in the layer A is SKYGREEN cube S2008, GN071 or 0603;
the PETG of the B layer and the C layer is at least one of K2012, KN200 and EB 062;
the PLA is at least one of 2003D and 2500 HP.
2. The method for preparing the PETG multilayer composite film for packaging according to claim 1, which is characterized by comprising the following steps:
(1) Respectively mixing the raw materials of each layer of the PETG multilayer composite film for packaging, and then carrying out melting plasticization in different extruders; then feeding the molten steel into a three-layer co-extrusion circular die head for melt molding to obtain a circular melt tube blank;
(2) The circular melt tube blank is subjected to vacuum sizing, cooling and molding, then is preheated in a hot water tank, and then is transversely blown up and longitudinally stretched;
(3) And carrying out irradiation treatment and heat treatment on the film subjected to blow molding, and finally rolling to obtain the PETG multilayer composite film for packaging.
3. The method for producing a PETG multilayer composite film for packaging according to claim 2, wherein:
the temperature of the three-layer co-extrusion circular die head in the step (1) is 180-185 ℃.
4. The method for producing a PETG multilayer composite film for packaging according to claim 2, wherein:
the radiation dose of the irradiation treatment in the step (3) is 100-300 kGy;
the heat treatment condition in the step (3) is that the heat treatment is carried out for 5-20 min at 80-90 ℃.
5. Use of the PETG multilayer composite film for packaging according to claim 1 in packaging materials.
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