CN112757730A - 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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CN112757730A
CN112757730A CN202110161046.1A CN202110161046A CN112757730A CN 112757730 A CN112757730 A CN 112757730A CN 202110161046 A CN202110161046 A CN 202110161046A CN 112757730 A CN112757730 A CN 112757730A
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layer
petg
multilayer composite
composite film
packaging
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CN112757730B (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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent
    • 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 (polyethylene terephthalate glycol) multilayer composite film for packaging and a preparation method thereof. The PETG multilayer composite film for packaging comprises three ABC film layers, wherein the layer A is a heat sealing layer, the layer B is a blocking layer, the layer C is a supporting layer, the component of the layer A is PETG, and the layer B is composed 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 comprises 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 elongation at break, and is green and 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 (polyethylene terephthalate glycol) multilayer composite film for packaging and a preparation method thereof.
Background
The food packaging material is used for manufacturing packaging containers, packaging decoration, packaging printing, packaging transportation and the like, and meets the requirements of product packaging. At present, materials commonly used for food packaging comprise plastics, glass, metal, wood, paper and the like, wherein the plastic packaging materials have the advantages of small specific gravity, light weight, easy processing, rich resources, less energy consumption, low cost, food protection and the like due to the characteristics of good plasticity, elasticity, insulativity, chemical inertness and the like, and are widely applied to food packaging. 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, the plastic materials for food packaging in China mainly include Polyethylene (PE), polypropylene (PP), Polyester (PET), polyvinylidene chloride (PVDC), Polycarbonate (PC), Polystyrene (PS), Polyamide (PA), polyvinyl alcohol (PVA), etc., but the plastic packaging materials also have certain defects and shortcomings: firstly, the stability is not good, the temperature is not high, and the deformation is easy; ② plastic raw materials and processing aids may cause pollution to packaged food, affecting human health, for example: a plasticizer; the petroleum-based plastic is used in a large amount and is difficult to degrade to cause white pollution, and great influence is caused on the environment.
With the increasing severity of environmental pollution, low carbon, energy conservation and environmental protection become the focus of global attention, and therefore green packaging is more and more valued and popularized. The green packaging material is a packaging material which does not cause harm to the natural environment and human health in the whole life cycle, can be recycled or automatically degraded in the later period without polluting the environment, and can effectively reduce the consumption of non-renewable resources. The degradability of plastic packaging materials is a research hotspot and difficulty of future packaging materials.
Currently, starch-based degradable materials, polylactic acid degradable plastics, water-soluble plastic films and the like are under development. The materials are more characterized in that a small amount of degradable materials are added into traditional plastics such as PP, PE and the like to achieve the purposes of reducing the cost and increasing the degradability of the plastics, but the problems of incomplete degradation are solved, some resin molecular frameworks are difficult to degrade within a long time, remain in the natural environment in the form of fragments or powder, and aggravate the difficulty of waste plastic recycling treatment. In addition, because the degradable plastic is a high molecular material prepared from 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 plastic (for example, starch-based degradable plastic has the defects of high brittleness and easy cracking), and 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 is influenced.
In recent years, regarding the research of 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 environmental protection of the food packaging materials is a requirement of sustainable development strategy in China, and it is necessary to provide a functional, safe and environment-friendly food packaging material.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims 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.
The invention further aims to provide application of the PETG multilayer composite film for packaging.
The purpose of the invention is realized by the following technical scheme:
the utility model provides a PETG multilayer composite film is used to packing, contains ABC three-layer rete, wherein, A layer is the heat-seal layer, and B layer is the barrier layer, and C layer is the supporting layer, and the component on A layer is PETG, and B layer comprises the following component by mass percent: 29-39.5% of PHA, 60-70% of PETG and 0.5-1% of nano tin dioxide, wherein the C layer comprises 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 (American Istmann) or 0603 (American Istmann);
the PETG of the B layer and the C layer is preferably at least one of K2012 (Korea SK), KN200 (Korea SK) and EB062 (American Istmann), and the PETG has high viscosity and good barrier property;
the PHA is preferably P34HB, 4HB is introduced into the PHA, the crystal regularity is damaged, the crystallinity is reduced, the mobility of a macromolecular chain is greatly improved, the crystallization rate is favorably 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 (American Nature Works) and 2500HP (American Nature Works);
the preparation method of the PETG multilayer composite film for packaging comprises the following steps:
(1) respectively mixing raw materials of each layer of the PETG multilayer composite film for packaging, and then carrying out melting plasticization in different extruders; then sending the mixture into a three-layer co-extrusion circular die head for melt molding to obtain a circular melt pipe blank;
(2) preheating the round melt pipe blank in a hot water tank after vacuum sizing and cooling forming, and then carrying out transverse blowing and longitudinal stretching;
(3) carrying out irradiation treatment and heat treatment on the film subjected to 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 blow-up ratio of the transverse blow-up in the step (2) is 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 in the step (3) is preferably carried out at 80-90 ℃ for 5-20 min;
a PETG multilayer composite film for packaging is prepared by the preparation method;
the PETG multilayer composite film for packaging is applied to a packaging material;
compared with the prior art, the invention has the following advantages and effects:
(1) the PETG multilayer composite film for packaging comprises three ABC film layers (figure 1), wherein the layer A is a heat sealing layer, the layer B is a blocking layer, the layer C is a supporting layer and does not need an adhesive layer, the heat sealing layer consists of PETG with good heat sealing strength and proper heat sealing temperature, the blocking layer consists of PETG and PHA with good gas blocking effect, the supporting layer consists of PLA and PETG, the three-layer structure comprises PETG, the content of 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 film layers are all green environment-friendly materials;
(2) 4HB is introduced into the P34HB type PHA, the crystal regularity is damaged, the crystallinity is reduced, the mobility of a macromolecular chain is greatly improved, the crystallization rate is favorably improved, the ductility of the macromolecular chain is further improved, and the mechanical property and the thermal stability are improved;
(3) according to the invention, the nano tin dioxide is added between the functional layers, wherein the nano material improves the antistatic capability of the film on one hand, and on the other hand, due to the existence of the metal tin element, the formation of large-size spherulites is reduced in the melt extrusion process of the PHA, the crystallization rate is improved, and the toughness and ductility of the PHA are improved;
(4) the invention can avoid the secondary crystallization phenomenon and the formation of spherulites of PHA in the room temperature process by the 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 improved;
(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 diagram of a PETG multilayer composite film for packaging provided by the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) PLA (2003D), P34HB (Shenzhen Yinmann), PETG SKYGREEN S2008 and EB062 were subjected to a drying and dehumidifying treatment before melt extrusion for later use:
(2) mix respectively each layer raw materials of PETG multilayer composite film for packing, wherein, the component of A layer (heat-seal layer) is PETG (PETGSKYGREEN S2008), and B layer (barrier layer) comprises the following component by mass percent: 34.2 percent of P34HB, 65 percent of PETG (EB 062) and 0.8 percent of nano tin dioxide, wherein 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 mixed, melting and plasticizing each layer in different extruders; then sending the mixture into a three-layer co-extrusion circular die head with the temperature of 180 ℃ for melt forming to obtain a circular melt pipe blank;
(3) preheating the circular melt pipe blank in a hot water tank after vacuum sizing and cooling forming, and injecting compressed air for transverse blowing and longitudinal stretching after preheating, wherein the blowing 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 Yinmann), PETGSKYGREEN S2008 and EB062 were subjected to a drying and dehumidifying treatment before melt extrusion for later use:
(2) mix respectively each layer raw materials of PETG multilayer composite film for packing, wherein, the component of A layer (heat-seal layer) is PETG (PETGSKYGREEN S2008), and B layer (barrier layer) comprises the following component by mass percent: 29% of P34HB, 70% of PETG (EB 062) and 1% of nano tin dioxide, wherein the 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 mixed, melting and plasticizing each layer in different extruders; then sending the mixture into a three-layer co-extrusion circular die head with the temperature of 180 ℃ for melt forming to obtain a circular melt pipe blank;
(3) preheating the circular melt pipe blank in a hot water tank after vacuum sizing and cooling forming, and injecting compressed air for transverse blowing and longitudinal stretching after preheating, wherein the blowing 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 Yinmann), PETGSKYGREEN S2008 and EB062 were subjected to a drying and dehumidifying treatment before melt extrusion for later use:
(2) mix respectively each layer raw materials of PETG multilayer composite film for packing, wherein, the component of A layer (heat-seal layer) is PETG (PETGSKYGREEN S2008), and B layer (barrier layer) comprises the following component by mass percent: 39.5 percent of P34HB, 60 percent of PETG (EB 062) and 0.5 percent 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 mixed, melting and plasticizing each layer in different extruders; then sending the mixture into a three-layer co-extrusion circular die head with the temperature of 185 ℃ for melt forming to obtain a circular melt pipe blank;
(3) preheating the circular melt pipe blank in a hot water tank after vacuum sizing and cooling forming, and injecting compressed air for transverse blowing and longitudinal stretching after preheating, wherein the blowing 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, the C layer (support layer) was prepared from PLA (2003D), the composition of the other layers was the same as in example 1, and the preparation method was the same as in example 1.
Comparative example 2
In this example, the layer B (barrier layer) is composed of the following components in mass percent: 40% P34HB and 60% PETG (EB 062), other layer compositions were the same as in example 1, and the preparation was the same as in example 1.
The thickness, tensile strength, elongation at break, heat-sealing temperature, heat-sealing strength, water vapor permeability, oxygen permeability, and the like of the PETG multilayer composite films for packaging prepared in examples 1 to 3 and comparative examples 1 to 2 were measured, respectively. The tensile strength and the elongation at break were performed according to the GB/T1040.3 method, the heat sealing performance was performed according to the BMSTT01 method, and the oxygen permeability and the like were performed according to the ASRM-related method.
The results are shown in Table 1.
TABLE 1 Properties of PETG multilayer composite films for packaging prepared in examples 1-3 and comparative examples 1-2
Figure DEST_PATH_IMAGE001
As can be seen from Table 1, the PETG multilayer composite film for packaging (comparative example 1) prepared by 100% PLA (2003D) of the C layer (supporting layer) is lower than the PETG multilayer composite films for packaging prepared in examples 1-3 in tensile strength and elongation at break, which shows that the PETG added in the C layer (supporting layer) can effectively improve the toughness and ductility of the film and simultaneously influences the barrier property of the film; the nano tin dioxide is not added in the comparative example 2, so that the barrier property of the film is not greatly influenced, but the addition of the tin dioxide can reduce the formation of large-size spherulites in PHA, improve the crystallization rate and further improve the tensile strength and the elongation at break of the PHA, and the table 1 shows that the tensile strength and the elongation at break of the multilayer composite film prepared in the comparative example 2 are obviously lower than those of the PETG multilayer composite film for assembly prepared in the examples 1-3.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1. The utility model provides a PETG multilayer composite film is used in packing which characterized in that contains ABC three-layer rete, wherein, A layer is the heat-seal layer, and B layer is the barrier layer, and C layer is the supporting layer, and the component on A layer is PETG, and B layer comprises the following component by mass percent: 29-39.5% of PHA, 60-70% of PETG and 0.5-1% of nano tin dioxide, wherein the C layer comprises the following components in percentage by mass: 70-80% of PLA and 20-30% of PETG.
2. The PETG multilayer composite film for packaging according to claim 1, wherein:
the PETG in the layer A is SKYGREEN S2008, GN071 or 0603.
3. The PETG multilayer composite film for packaging according to claim 1, wherein:
the PETG of the B layer and the C layer is preferably at least one of K2012, KN200 and EB 062.
4. The PETG multilayer composite film for packaging according to claim 1, wherein:
the PHA is P34 HB.
5. The PETG multilayer composite film for packaging according to claim 1, wherein:
the PLA is at least one of 2003D and 2500 HP.
6. The preparation method of the PETG multilayer composite film for packaging as claimed in any one of claims 1-5, characterized by comprising the following steps:
(1) respectively mixing raw materials of each layer of the PETG multilayer composite film for packaging, and then carrying out melting plasticization in different extruders; then sending the mixture into a three-layer co-extrusion circular die head for melt molding to obtain a circular melt pipe blank;
(2) preheating the round melt pipe blank in a hot water tank after vacuum sizing and cooling forming, and then carrying out transverse blowing and longitudinal stretching;
(3) and (3) 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.
7. The method for preparing PETG multilayer composite film for packaging according to claim 6, is characterized in that:
the temperature of the three-layer co-extrusion circular die head in the step (1) is 180-185 ℃.
8. The method for preparing PETG multilayer composite film for packaging according to claim 6, is characterized in that:
the radiation dose of the irradiation treatment in the step (3) is 100-300 kGy;
the heat treatment in the step (3) is carried out for 5-20 min at the temperature of 80-90 ℃.
9. Use of the PETG multilayer composite film for packaging as claimed in claims 1-5 in a packaging material.
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