CN114407461A - Biaxially oriented polyethylene base film with high surface energy - Google Patents

Biaxially oriented polyethylene base film with high surface energy Download PDF

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CN114407461A
CN114407461A CN202210111151.9A CN202210111151A CN114407461A CN 114407461 A CN114407461 A CN 114407461A CN 202210111151 A CN202210111151 A CN 202210111151A CN 114407461 A CN114407461 A CN 114407461A
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layer
polyethylene
base film
equal
transition
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Inventor
唐敏艳
俞晓琴
俞春良
徐涛
夏嘉良
高学文
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Jiangsu Caihua Packaging Group Integrated Packaging Technology Co ltd
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Jiangsu Caihua Packaging Group Integrated Packaging Technology 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B27/065—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 foam
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • 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
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • B32B2250/05—5 or more 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/025—Polyolefin

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)

Abstract

A biaxially oriented polyethylene base film with high surface energy is prepared by coextrusion and biaxial orientation processes of at least five-layer structures, wherein the five-layer structures are sequentially arranged in the thickness direction of the base film: the outer layer is a high surface energy layer which can improve the high surface adhesive force between the base film and other films or layers through a chemical bond form, and the hook chain layer is transition of polarity and compatibility between the main stretching layer and outer layer materials; the main stretching layer is a functional layer which bears a main stretching task in the process of biaxial stretching processing; the transition layer is the transition of the melting temperature between the main stretching layer and the inner layer material; the inner layer is a heat sealing layer. According to the invention, the surface layer is endowed with polarity to obtain the base film with high surface energy, so that the high adhesion of the surface of the PE base material is realized. The design that the weight of the polyethylene is more than or equal to 90 percent of the total weight of the base film meets the environmental protection requirements of easy recovery and easy recycling of products.

Description

Biaxially oriented polyethylene base film with high surface energy
Technical Field
The invention relates to the field of polyethylene films, in particular to a biaxially oriented polyethylene base film with high surface energy. The surface energy of the polyethylene base film can reach 38 dyne/cm or more.
Background
The difficulty in recycling waste plastics, particularly functional flexible packages, is a problem which is highly concerned and urgently solved in the world. The design concept of high-barrier functional single material is the preferred direction for the development of new materials for flexible packaging in the world.
The commercially available high-barrier functional film usually takes a polyester film as a base film, and utilizes the good polarity of a polyester material to meet the sufficient adhesive force and durability of the base film, a barrier coating and a barrier evaporation layer so as to obtain stable, controllable and durable barrier performance.
Polyethylene is a non-polar material with low surface energy, hydrophobic and inert surface, has poor cohesiveness, antistatic property and hydrophilicity, and has poor compatibility with polar polymers or inorganic fillers, and objective factors limit the polyethylene base film to obtain high barrier property through energization. Therefore, when it is desired to impart high barrier to a polyethylene single-material base film for composite, barrier coating or barrier evaporation, the high surface energy of the film is the first factor to be considered, and in general, the surface energy of the film can be characterized by surface tension, which requires that the surface tension of the base film reaches 38 dyne/cm or higher. While the surface tension of polyethylene is only 31 dynes/cm or even lower.
The prior art mainly increases the surface tension of the base film by surface treatment technology. The more common ways are corona discharge treatment and polar undercoating. The corona discharge adopts high-frequency high-voltage or medium-frequency high-voltage discharge to treat the surface of the plastic, so that the surface of the plastic is porous and activated, the adhesion of the surface of the plastic film to a coating or a plating layer is improved, and the surface energy of the film is improved; however, corona treatment, although it can increase the surface energy, is very unstable and even disappears after a few days of storage, which is very inconvenient for daily production. The polar base coat is formed by coating the surface of plastic, which is similar to the process of glue coating, so that the adhesion of the barrier coating on the surface of the PE substrate is improved. However, the primer coating also has the problem of environmental protection except for increasing the production process and the solvent problem of the coating, and does not meet the low-carbon and VOCs emission requirements advocated by our country. Therefore, how to effectively improve the surface energy of the polyethylene film is a key technology which needs to be solved urgently in the development of recyclable and reusable functional single-material materials for flexible packages.
In view of this, how to design a biaxially oriented polyethylene-based film with high surface energy is the subject of the present invention.
Disclosure of Invention
The invention provides a biaxially oriented polyethylene base film with high surface energy, which aims to solve the problem of low surface energy of the polyethylene base film through structural design.
In order to achieve the purpose, the invention adopts the technical scheme that:
a biaxially oriented polyethylene base film having a high surface energy, the polyethylene base film being made by a coextrusion and biaxial orientation process from at least the following five-layer structure, the five-layer structure being in the order of the thickness direction of the polyethylene base film: skin, hook chain layer, main tensile layer, transition layer and inlayer, its characterized in that:
the outer layer is a high surface energy layer capable of enhancing high surface adhesion between the base film and other films or layers by chemical bond formation, the outer layer has a surface tension greater than or equal to 38 dynes/cm, and the material of the outer layer comprises a polymer containing at least one of the following functional groups:
a carboxyl group;
a hydroxyl group;
an amide group;
an ester group;
the functional groups in the polymer are arranged in order of magnitude of polarity as follows: carboxyl > hydroxyl > amido > ester;
the weight of the outer layer is less than or equal to 10% of the total weight of the polyethylene-based film;
the hook chain layer refers to the transition of polarity and compatibility between the main stretching layer and the outer layer material so as to meet the requirement of interface bonding;
the material of the hook chain layer comprises modified polyethylene containing at least one of the following functional groups:
a carboxyl group;
an ester group;
the functional groups in the modified polyethylene are arranged according to the polarity size sequence as follows: carboxyl > ester group;
the polarity of the functional group used in the modified polyethylene is greater than or equal to the polarity of the functional group in the polymer used in the outer layer;
the number of the hook chain layers is at least one;
the main stretching layer is a functional layer which bears a main stretching task in a biaxial stretching processing process, the weight of the main stretching layer is more than or equal to 40% of the total weight of the polyethylene base film, the main stretching layer is made of polyethylene, and the main stretching layer is at least one layer;
the transition layer is the transition of melting temperature between the main stretching layer and the inner layer material so as to meet the processing requirement, the transition layer is made of polyethylene, and the transition layer is at least one layer;
the inner layer is a heat sealing layer and made of polyethylene, and the weight of the inner layer is less than or equal to 20% of the total weight of the polyethylene base film;
the weight of the polyethylene in the polyethylene-based film is greater than or equal to 90% of the total weight of the polyethylene-based film.
Wherein the outer layer of the polyethylene-based film is corona treated to assist in increasing the surface energy.
Wherein, the other film or layer refers to a film or layer attached to the outer layer surface of the base film by means of evaporation, coating, compounding and printing processes.
Wherein the density of the polyethylene in the primary tensile layer is greater than or equal to the average density of the polyethylene in the transition layer.
Wherein the average density of the polyethylene in the transition layer is greater than or equal to the average density of the polyethylene in the inner layer.
Wherein, the base film can be directly recycled by a physical recycling method and reused.
Wherein the heat seal strength of the base film is greater than or equal to 5N/15mm (i.e., 5N/15mm, N means Newton, 15mm means millimeter width).
The following is a related explanation of the technical scheme of the invention:
1. surface energy is a measure of the breakdown of chemical bonds between molecules when creating a surface of a substance. In solid physics, surface atoms have more energy than atoms inside a substance, and therefore, according to the principle of energy minimization, atoms tend spontaneously to the inside of a substance rather than to the surface. Another definition of surface energy is the excess energy at the surface of a material relative to the interior of the material. The surface free energy is the embodiment of intermolecular forces on the surface of an object, is closely related to the wettability of the solid surface, and has an important role in surface chemistry.
2. The plating layer/coating and the base film can be combined together through the actions of forming hydrogen bonds and chemical bonds through mechanical combination, physical adsorption and the like, mutual diffusion and the like, and the adhesion force generated by the actions determines the interlayer adhesion force between the plating film and the base film.
3. The surface energy is usually related to the polarity of the molecule, the polarity of the molecule is large, the surface energy is generally relatively higher, the polarity of the molecule is small, and the surface energy is generally lower.
4. The organic chemical reaction mainly occurs on functional groups, which play a determining role on the properties of organic matters, such as carbon-carbon double bonds, hydroxyl groups, carboxyl groups, amide groups, ester groups and the like.
The following is the polar size ordering of common functional groups:
alkane (-CH)3，—CH2-) < olefin (-CH = CH-) < ester (-COOR) < amide (-NHCO-CH)3) < alcohols (-OH) < carboxylic acids (-COOH).
5. The following table shows the values of the wetting tension (temperature: 20 ℃ C.) of a conventional plastic film:
Figure 885281DEST_PATH_IMAGE001
6. the wettability of a solid surface is determined by its chemical composition and microstructure. The greater the free energy of a solid surface, the more readily wetted by a liquid and vice versa. Thus, the search for and the preparation of solid surfaces with high surface free energy are a prerequisite for the preparation of hydrophilicity. .
Researches show that main factors influencing the surface wettability of the material comprise material surface energy, surface roughness and a surface micro/nano structure, the technical scheme adopted by the invention achieves the aim of the invention by improving the surface energy of the material, and particularly improves the surface energy of a base film in a chemical bond form, so that the adhesive force between the base film and other films or coatings or plating layers is improved.
The design principle and the effect of the invention are as follows:
1. according to the technical scheme, the outer layer of the polyethylene base film is endowed with polarity, so that high surface energy is obtained, and high adhesion of the barrier coating or coating on the surface of the PE base material is realized.
2. In the PE base film structure, the surface tension (31 dyne/cm) of the inner layer material is lower than the surface tension (more than 38 dyne/cm) of the outer layer material, and the surface wetting of the outer layer of the PE base film is good, so that a plating layer or a coating can be firmly adhered to the surface of the PE base film and is not easy to adhere to the inner layer.
3. In the PE base film structure, the hook chain layer is arranged between the main stretching layer and the outer layer, so that the transition of polarity and compatibility between the material of the main stretching layer and the material of the outer layer is realized, and the reliable binding force between interfaces is ensured.
4. In the PE base film structure, the weight of the polyethylene is more than or equal to 90 percent of the total weight of the polyethylene base film, so that the environmental protection requirements of easy recovery and easy reutilization of products are met.
5. The invention adopts a co-extrusion biaxial stretching production process of one-step molding, realizes the green packaging requirements of decrement, low carbon and no VOCs emission, and conforms to the environmental protection requirements of low carbon, clean production, easy recovery and easy recycling.
Detailed Description
The invention is further described below with reference to the following examples:
the chinese meanings of the english symbols referred in this embodiment are respectively:
1. polar polymer: ester group (EVA is ethylene-vinyl acetate copolymer, EAA is ethylene methyl acrylate copolymer, EMAA is ethylene methyl methacrylate copolymer), hydroxyl group (EVOH is ethylene-vinyl alcohol copolymer), amide group (PA 6 is nylon 6), carboxyl group (maleic anhydride grafted ethylene copolymer).
2. Non-polar polymer: PE is polyethylene, LDPE is low density polyethylene, LLDPE is linear low density polyethylene, EPE is polyethylene foam (in the embodiment, EPE is PE on-line foam, namely foam in the extrusion processing process), MLLDPE is metallocene linear low density polyethylene, HDPE is high density polyethylene, MPE is metallocene polyethylene, and TPU is thermoplastic polyurethane elastomer rubber.
The following table is a typical density of the materials used in the examples:
Figure 398826DEST_PATH_IMAGE002
example 1:
Figure 116247DEST_PATH_IMAGE003
the polarity of the functional group (carboxyl) contained in the hook chain layer is larger than that of the functional group (hydroxyl) contained in the outer layer;
the high surface layer has a surface tension of 50 dynes/cm and greater than 38 dynes/cm.
Example 2:
Figure 777035DEST_PATH_IMAGE004
the polarity of the functional group (carboxyl) contained in the hook chain layer is larger than that of the functional group (amido) contained in the outer layer;
the high surface layer has a surface tension of 46 dynes/cm and greater than 38 dynes/cm.
Example 3:
Figure 981620DEST_PATH_IMAGE005
the polarity of the functional group (ester group) contained in the hook chain layer is equal to that of the functional group (ester group) contained in the outer layer;
the high surface layer has a surface tension of 40 dynes/cm and greater than 38 dynes/cm.
Example 4:
Figure 194296DEST_PATH_IMAGE006
the polarity of the functional group (ester group) contained in the hook chain layer is equal to that of the functional group (ester group) contained in the outer layer;
the high surface layer has a surface tension of 40 dynes/cm and greater than 38 dynes/cm.
This embodiment is heat sealable.
Example 5:
Figure 399012DEST_PATH_IMAGE007
the polarity of the functional group (ester group) contained in the hook chain layer is equal to that of the functional group (ester group) contained in the outer layer;
the high surface layer has a surface tension of 40 dynes/cm and greater than 38 dynes/cm.
This embodiment is heat sealable.
Example 6:
Figure 50442DEST_PATH_IMAGE008
the polarity of the functional group (carboxyl) contained in the hook chain layer is larger than that of the functional group (hydroxyl) contained in the outer layer;
the high surface layer has a surface tension of 40 dynes/cm and greater than 38 dynes/cm.
Example 7:
Figure 657004DEST_PATH_IMAGE009
the polarity of the functional group (ester group) contained in the hook chain layer is equal to that of the functional group (ester group) contained in the outer layer;
the high surface layer has a surface tension of 40 dynes/cm and greater than 38 dynes/cm.
Example 8:
Figure 915947DEST_PATH_IMAGE010
the polarity of the functional group (ester group) contained in the hook chain layer is equal to that of the functional group (ester group) contained in the outer layer;
the high surface layer has a surface tension of 42 dynes/cm and greater than 38 dynes/cm.
Example 9:
Figure 143314DEST_PATH_IMAGE011
the polarity of the functional group (ester group) contained in the hook chain layer is equal to that of the functional group (ester group) contained in the outer layer;
the high surface layer has a surface tension of 42 dynes/cm and greater than 38 dynes/cm.
It is known to those skilled in the art that EPE (polyethylene blown) has a density lower than the typical density.
The above embodiments all can increase the surface energy by corona.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (7)

1. A biaxially oriented polyethylene base film having a high surface energy, the polyethylene base film being made by a coextrusion and biaxial orientation process from at least the following five-layer structure, the five-layer structure being in the order of the thickness direction of the polyethylene base film: skin, hook chain layer, main tensile layer, transition layer and inlayer, its characterized in that:
the outer layer is a high surface energy layer capable of enhancing high surface adhesion between the base film and other films or layers by chemical bond formation, the outer layer has a surface tension greater than or equal to 38 dynes/cm, and the material of the outer layer comprises a polymer containing at least one of the following functional groups:
a carboxyl group;
a hydroxyl group;
an amide group;
an ester group;
the functional groups in the polymer are arranged in order of magnitude of polarity as follows: carboxyl > hydroxyl > amido > ester;
the weight of the outer layer is less than or equal to 10% of the total weight of the polyethylene-based film;
the hook chain layer refers to the transition of polarity and compatibility between the main stretching layer and the outer layer material so as to meet the requirement of interface bonding;
the material of the hook chain layer comprises modified polyethylene containing at least one of the following functional groups:
a carboxyl group;
an ester group;
the functional groups in the modified polyethylene are arranged according to the polarity size sequence as follows: carboxyl > ester group;
the polarity of the functional group used in the modified polyethylene is greater than or equal to the polarity of the functional group in the polymer used in the outer layer;
the number of the hook chain layers is at least one;
the main stretching layer is a functional layer which bears a main stretching task in a biaxial stretching processing process, the weight of the main stretching layer is more than or equal to 40% of the total weight of the polyethylene base film, the main stretching layer is made of polyethylene, and the main stretching layer is at least one layer;
the transition layer is the transition of melting temperature between the main stretching layer and the inner layer material so as to meet the processing requirement, the transition layer is made of polyethylene, and the transition layer is at least one layer;
the inner layer is a heat sealing layer and made of polyethylene, and the weight of the inner layer is less than or equal to 20% of the total weight of the polyethylene base film;
the weight of the polyethylene in the polyethylene-based film is greater than or equal to 90% of the total weight of the polyethylene-based film.
2. Polyethylene-based film according to claim 1, characterized in that: the outer layer of the polyethylene-based film is corona treated to assist in increasing the surface energy.
3. Polyethylene-based film according to claim 1, characterized in that: the other film or layer is a film or layer attached to the outer layer surface of the base film by means of evaporation, coating, compounding and printing processes.
4. Polyethylene-based film according to claim 1, characterized in that: the density of the polyethylene in the primary tensile layer is greater than or equal to the average density of the polyethylene in the transition layer.
5. Polyethylene-based film according to claim 1, characterized in that: the average density of the polyethylene in the transition layer is greater than or equal to the average density of the polyethylene in the inner layer.
6. Polyethylene-based film according to one of claims 1 to 5, characterized in that: the base film can be directly recycled and reused by a physical recycling method.
7. Polyethylene-based film according to one of claims 1 to 5, characterized in that: the heat seal strength of the base film is greater than or equal to 6N/15 mm.
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