CN111516344B - Biaxially oriented polyamide film and preparation method thereof - Google Patents
Biaxially oriented polyamide film and preparation method thereof Download PDFInfo
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- CN111516344B CN111516344B CN202010364781.8A CN202010364781A CN111516344B CN 111516344 B CN111516344 B CN 111516344B CN 202010364781 A CN202010364781 A CN 202010364781A CN 111516344 B CN111516344 B CN 111516344B
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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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- 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
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/582—Tearability
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
Abstract
The invention provides a biaxially oriented polyamide film and a preparation method thereof, wherein the biaxially oriented polyamide film comprises a three-layer co-extrusion biaxially oriented nylon film, wherein A, B, C layers are sequentially arranged from top to bottom; the layer A and the layer C are both composed of 67-79.5% of nylon 6, 20-30% of special nylon composition and 0.5-3% of anti-sticking nylon master batch; the layer B consists of 65 to 85 percent of nylon 6 and 15 to 35 percent of special nylon composition; the special nylon composition contains MXD6-PA66 copolymer, long carbon chain nylon, nylon copolymer and compatilizer. The film has a linear easy-tearing effect, and even if the bag is compounded with films such as PP, PE and the like, the film also has linear tearing performance.
Description
Technical Field
The invention relates to the technical field of film materials, in particular to a biaxially oriented polyamide film and a preparation method thereof.
Background
With the development of socio-economy, people are pursuing more and more convenience of life, especially in the field of packaging. The existing product for packaging food, medicine and the like usually adopts PE, PP and other materials as a heat sealing layer, and the outer layer adopts PA, PET and other materials, so that the bag with the structure has the characteristics of high sealing strength and excellent barrier property, but has the problems of large tearing resistance and incapability of being torn straightly along scratches during use, thereby causing certain troubles in life. Particularly for the elderly and children, it is more desirable that the product is easily torn due to physical strength. Accordingly, there is an increasing demand for films having oxygen barrier properties and linear tearability, and research thereon is being conducted.
Patent CN105778488A, published Japanese 2016.07.20, discloses a linear easy-to-tear polyamide film, which comprises 39-81 parts of PA6, 8-30 parts of MXD6, 5-10 parts of softening agent, 3-20 parts of PA6/MXD6 secondary material and 1-3 parts of MXD 6-g-MAH.
Patent CN109890609A, published japanese patent No. 2019.06.14, discloses an easily tearable aluminum vapor-deposited biaxially stretched film comprising at least an aluminum vapor-deposited layer (a)/a barrier layer (B)/an adhesive layer (C)/a polypropylene layer (D) laminated in this order, wherein the barrier layer (B) comprises a mixture of a polyamide (a) and an amorphous polyamide (B), the polyamide (a) is a polyamide comprising a diamine unit and a dicarboxylic acid unit, the diamine unit contains 70 mol% or more of a structural unit derived from xylylenediamine, the dicarboxylic acid unit contains 70 mol% or more of a structural unit derived from an α, ω -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and the barrier layer (B) contains 30 to 70 mass% of the polyamide (a) and 30 to 70 mass% of the amorphous polyamide (B).
Although the related products of the straight-line easy-tearing film are disclosed, the types of the products are still relatively few, and the market demands are difficult to meet. Therefore, the development of novel linear easy-to-tear film products is still the appeal of the industry.
Disclosure of Invention
In order to solve the problems that related products of the existing linear easy-to-tear film are still few in types and are difficult to meet the market demand in the background art, the invention provides a biaxially oriented polyamide film which comprises three layers of co-extruded biaxially oriented nylon films, wherein the A, B, C layers are sequentially arranged from top to bottom; the layer A and the layer C are respectively composed of 67-79.5% of nylon 6, 20-30% of special nylon composition and 0.5-3% of anti-sticking nylon master batch by mass percentage; the layer B consists of 65 to 85 percent of nylon 6 and 15 to 35 percent of special nylon composition;
the special nylon composition contains MXD6-PA66 copolymer, long carbon chain nylon, nylon copolymer and compatilizer.
In the prior art, special nylon MXD6 is added into a film material to change the internal molecular morphology of nylon so that the nylon film has linear tearability. However, in actual production, it is found that although special nylon MXD6 is added into a nylon film material, although the nylon film material has linear easy-tear property, MXD6 has high rigidity, is easy to rupture a film, reduces the puncture resistance and flexibility of the film, is easy to cause the problems of pinholes and the like in subsequent processing, has obvious bow effect, and causes the yield of the linear easy-tear nylon film to be relatively low. The special nylon MXD6 is replaced by the special nylon composition containing the MXD6-PA66 copolymer, the long carbon chain nylon, the nylon copolymer and the compatilizer, so that the problems of the MXD6 can be effectively solved, and the special nylon composition has excellent linear tearing performance.
Furthermore, the proportion of the PA66 component in the MXD6-PA66 copolymer is 1-10%.
Further, the long carbon chain nylon is an odd-even long carbon chain nylon formed by polycondensation of alpha, omega-straight chain aliphatic dicarboxylic acid with the carbon number of 5-20 and alpha, omega-straight chain aliphatic diamine with the carbon number of 5-20, or an even long carbon chain nylon formed by polycondensation of alpha, omega-straight chain aliphatic dicarboxylic acid with the carbon number of 5-20 and alpha, omega-straight chain aliphatic diamine with the carbon number of 5-20; the melting point of the long carbon chain nylon is 175-240 ℃.
Further, the nylon copolymer is at least one of a PA66/PA6 copolymer, an MXD6/PA6 copolymer and an MXD6/PA1010 copolymer.
Further, the compatilizer is at least one of MXD6-g-MAH and MXD 6-g-GMA.
Further, the content ratio of the MXD6-PA66 copolymer to the long carbon chain nylon to the nylon copolymer to the compatilizer is 6-8: 3-4: 2-3: 1 to 2.
Further, at least one side of the A and C layers is corona treated, and the corona value is more than 50 dyn.
Further, the thickness of the biaxially oriented polyamide film is 10-30 μm, wherein the thickness of the layer A and the layer C is 1.5-4 μm.
Further, the biaxially oriented polyamide film has linear tear properties in the MD direction.
The invention also provides a preparation method of the biaxially oriented polyamide film, which comprises the following steps:
step one, mixing the components in the A, B, C layers according to a proportion respectively, and dispersing the components uniformly by a high-speed stirrer;
step two, melting and co-extruding the uniformly mixed raw materials in the step one through three extruders, and casting the melt to a chilled roll quenching casting sheet with the surface temperature of 15-35 ℃ through a T-shaped mouth die;
step three, humidifying the casting sheet in the step two in a 40-75 ℃ water tank for 1-2 minutes, drying the residual moisture on the surface of the humidified casting sheet by using an air knife, and synchronously or in a distributed manner and stretching;
and step four, performing heat setting treatment on the film obtained in the step three at the setting temperature of 180-215 ℃, performing corona treatment on at least one of the layer A and the layer C, and then rolling and cutting to obtain the linear easy-to-tear nylon film.
Furthermore, in the third step, the stretching temperature is 130-205 ℃, and the stretching magnification is 2.5 multiplied by 2.5-3.5 multiplied by 3.5.
The biaxially oriented polyamide film provided by the invention has an excellent linear easy-tearing effect, and even a bag compounded with films such as PP (polypropylene), PE (polyethylene) and the like can also have good linear tearing performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 is a schematic structural view of a linear easy-tear nylon film provided by the present invention;
FIG. 2 is a schematic diagram of the evaluation of the linear tear properties of the film. Reference numerals:
10A layer, 20B layer, 30C layer
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method of the biaxially oriented polyamide film provided by the embodiment of the invention comprises the following steps:
step one, mixing the components in the A, B, C layers according to a proportion respectively, and dispersing the components uniformly by a high-speed stirrer;
step two, melting and co-extruding the uniformly mixed raw materials in the step one through three extruders, and casting the melt to a chilled roll quenching casting sheet with the surface temperature of 15-35 ℃ through a T-shaped mouth die;
step three, humidifying the casting sheet in the step two in a 40-75 ℃ water tank for 1-2 minutes, drying the residual moisture on the surface of the humidified casting sheet by using an air knife, and synchronously or distributively stretching at the stretching temperature of 130-205 ℃ at the stretching ratio of 2.5 multiplied by 2.5-3.5 multiplied by 3.5;
and step four, performing heat setting treatment on the film obtained in the step three at the setting temperature of 180-215 ℃, performing corona treatment on at least one of the layer A and the layer C, and then rolling and cutting to obtain the linear easy-to-tear nylon film.
Example 1
As shown in FIG. 1, a biaxially oriented polyamide film having a thickness of 15 μm and thicknesses of A and C layers of 2 μm.
The layer A and the layer C are respectively composed of 69.5 percent of nylon 6, 30 percent of special nylon composition and 0.5 percent of anti-sticking nylon master batch by mass percentage; the layer B consists of 85 percent of nylon 6 and 15 percent of special nylon composition;
the special nylon composition consists of MXD6-PA66 copolymer, PA512, PA66/PA6 copolymer and MXD6-g-MAH, and the content ratio is 6: 4: 3: 1.
example 2
As shown in FIG. 1, a biaxially oriented polyamide film having a thickness of 15 μm and thicknesses of A and C layers of 3 μm.
The layer A and the layer C consist of 79 percent of nylon 6, 20 percent of special nylon composition and 1 percent of anti-sticking nylon master batch in percentage by mass; the layer B consists of 65 percent of nylon 6 and 35 percent of special nylon composition;
the special nylon composition consists of MXD6-PA66 copolymer, PA612, MXD6/PA6 copolymer and MXD6-g-MAH, and the content ratio is 7: 3: 3: 1.
example 3
As shown in FIG. 1, a biaxially oriented polyamide film was 15 μm thick and the thickness of the A and C layers was 4 μm.
The layer A and the layer C consist of 77 percent of nylon 6, 20 percent of special nylon composition and 3 percent of anti-sticking nylon master batch in percentage by mass; the layer B consists of 70 percent of nylon 6 and 30 percent of special nylon composition;
the special nylon composition consists of MXD6-PA66 copolymer, PA1616, MXD6/PA1010 copolymer and MXD6-g-GMA, and the content ratio is 8: 3: 2: 2.
comparative example 1
A biaxially oriented polyamide film having a film structure of A, B, C layers in this order from top to bottom and having a thickness of 15 μm and a thickness of 3 μm for A and C layers.
The layer A and the layer C consist of 72 percent of nylon 6, 25 percent of MXD6 and 3 percent of anti-sticking nylon master batch in percentage by mass; layer B consisted of 70% nylon 6 and 30% MXD6 composition.
The preparation method refers to the preparation method of the embodiment.
Comparative example 2
The biaxially oriented polyamide film has a film structure comprising A, B, C layers from top to bottom, the thickness of the film structure is 15 μm, and the thickness of the A and C layers is 2 μm.
The A layer and the C layer consist of 77 percent of nylon 6, 20 percent of MXD6-PA66 copolymer and 3 percent of anti-sticking nylon master batch in percentage by mass; the B layer was composed of 75% nylon 6 and 25% MXD6-PA66 copolymer.
The preparation method refers to the preparation method of the embodiment.
The present invention tests the relevant performance of the above examples and comparative examples, and the specific result data is shown in table 1.
Evaluation of straight-line tear Performance: cutting a film with length (MD direction) and width (TD direction) of 220mm × 40mm, cutting a tear notch with length of 20mm in the middle of the film, tearing the film at uniform speed along the direction of the crack for 200mm, and measuring the maximum distance of the tear notch from the center line of the tear opening during tearing, namely the deviation displacement SβAs shown in fig. 2. The measurement was carried out on 25 films, if the tear displacement S0An average deviation displacement S at 200mmβWhen the thickness is less than or equal to 6mm, the straight tearing property of the film is good (marked as a), and on the contrary, the straight tearing property of the film is poor (marked as gamma).
Yield evaluation: if the yield of the nylon film for preparing the nylon composite film (PA/PE) with linear tearing performance is less than 90%, the yield is low (recorded as □); if the yield of the nylon film for preparing the nylon composite film (PA/PE) with linear tearing performance is more than 90%, the yield is high (marked as delta). Puncture resistance strength: the film is cut into a specification of 100mm x 100mm, the surface of the film is required to be flat, and the film is not scratched or cut and the like, the puncture resistance strength of the film is tested on a universal tensile testing machine by adopting a fixture of a steel needle with the size of 1mm at the temperature of 23 ℃ and the relative humidity of 50%, and the testing speed is 50mm/mi n.
TABLE 1
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Linear tearability | ▲ | ▲ | ▲ | ▲ | ▲ |
| Yield of | Δ | Δ | Δ | □ | □ |
| Puncture strength (N) | 9.2 | 10.1 | 9.5 | 8.2 | 8.4 |
As can be seen from Table 1, the films prepared in examples 1-3 of the present invention all had MD direction linear tearability and the yield evaluation was high; the films of comparative examples 1 and 2 also had MD direction linear tear properties, but the yield evaluation was low. Therefore, the special nylon composition containing the MXD6-PA66 copolymer, the long carbon chain nylon, the nylon copolymer and the compatilizer can improve the yield.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. A biaxially oriented polyamide film characterized by: comprises three layers of co-extruded biaxially oriented nylon films, wherein A, B, C layers are sequentially arranged from top to bottom; the layer A and the layer C are respectively composed of 67-79.5% of nylon 6, 20-30% of special nylon composition and 0.5-3% of anti-sticking nylon master batch by mass percentage; the layer B consists of 65 to 85 percent of nylon 6 and 15 to 35 percent of special nylon composition;
the special nylon composition contains MXD6-PA66 copolymer, long carbon chain nylon, nylon copolymer and compatilizer;
the long carbon chain nylon is odd-even long carbon chain nylon formed by the polycondensation of alpha, omega-straight chain aliphatic dicarboxylic acid with the carbon atom number of 5-20 and alpha, omega-straight chain aliphatic diamine with the carbon atom number of 5-20, or even long carbon chain nylon formed by the polycondensation of alpha, omega-straight chain aliphatic dicarboxylic acid with the carbon atom number of 5-20 and alpha, omega-straight chain aliphatic diamine with the carbon atom number of 5-20, wherein the melting point of the long carbon chain nylon is 175-240 ℃;
the nylon copolymer is at least one of a PA66/PA6 copolymer, an MXD6/PA6 copolymer and an MXD6/PA1010 copolymer;
the compatilizer is at least one of MXD6-g-MAH and MXD 6-g-GMA;
the content ratio of the MXD6-PA66 copolymer to the long carbon chain nylon to the nylon copolymer to the compatilizer is 6-8: 3-4: 2-3: 1 to 2.
2. The biaxially stretched polyamide film according to claim 1, wherein: the PA66 component in the MXD6-PA66 copolymer accounts for 1-10%.
3. The biaxially stretched polyamide film according to claim 1, wherein: at least one side of the A and C layers is subjected to corona treatment, and the corona value is more than 50 dyn.
4. The biaxially stretched polyamide film according to claim 1, wherein: the biaxially oriented polyamide film has linear tear properties in the MD direction.
5. A method for producing a biaxially oriented polyamide film according to any one of claims 1 to 4, wherein: the method comprises the following steps:
step one, mixing the components in the A, B, C layers according to a proportion respectively, and dispersing the components uniformly by a high-speed stirrer;
step two, melting and co-extruding the uniformly mixed raw materials in the step one through three extruders, and casting the melt to a chilled roll quenching casting sheet with the surface temperature of 15-35 ℃ through a T-shaped mouth die;
step three, humidifying the casting sheet in the step two in a 40-75 ℃ water tank for 1-2 minutes, drying the residual moisture on the surface of the humidified casting sheet by using an air knife, and stretching synchronously or step by step;
and step four, carrying out heat setting treatment on the film obtained in the step three at the setting temperature of 180-215 ℃, carrying out corona treatment on at least one of the layer A and the layer C, and then rolling and cutting to obtain the biaxially oriented polyamide film.
6. The method for producing a biaxially oriented polyamide film according to claim 5, wherein: in the third step, the stretching temperature is 130-205 ℃, and the stretching magnification is 2.5 multiplied by 2.5-3.5 multiplied by 3.5.
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| CN112590338A (en) * | 2020-12-07 | 2021-04-02 | 厦门长塑实业有限公司 | Ultraviolet-resistant biaxially oriented nylon film with direct tearing property and preparation method thereof |
| CN114907688B (en) * | 2021-02-09 | 2024-04-05 | 上海凯赛生物技术股份有限公司 | Long carbon chain polyamide 5X film and preparation method thereof |
| CN114228292B (en) * | 2021-12-13 | 2022-09-30 | 厦门长塑实业有限公司 | High-shrinkage biaxial oriented polyamide film and preparation method and application thereof |
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| JP4601351B2 (en) * | 2004-07-23 | 2010-12-22 | グンゼ株式会社 | Polyamide-based multilayer film and method for producing the same |
| CN102190120B (en) * | 2010-03-04 | 2013-12-11 | 厦门长天企业有限公司 | Polyamide film and preparation method thereof |
| CN105778488B (en) * | 2016-05-17 | 2018-02-09 | 厦门长塑实业有限公司 | A kind of straight line easily tears polyamide film and preparation method thereof |
| WO2018083962A1 (en) * | 2016-11-04 | 2018-05-11 | 三菱瓦斯化学株式会社 | Easily tearable aluminum-vapor-deposited biaxially oriented film |
| CN108481866B (en) * | 2018-04-04 | 2019-08-30 | 厦门长塑实业有限公司 | A kind of heat sealable BON biaxially oriented nylon film and preparation method thereof |
| CN108515762B (en) * | 2018-04-08 | 2019-09-17 | 厦门长塑实业有限公司 | A kind of puncture-resistant BON biaxially oriented nylon film of three-decker and preparation method thereof |
| CN110524992B (en) * | 2019-09-20 | 2021-07-30 | 厦门长塑实业有限公司 | Nylon film for compounding aluminum plastic film of lithium battery and preparation method thereof |
| CN110641118B (en) * | 2019-10-17 | 2021-07-27 | 厦门长塑实业有限公司 | High-barrier scratch-resistant biaxially oriented polyamide film and preparation method thereof |
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