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CN111497405B - High-barrier type linear easy-to-tear nylon film and preparation method thereof - Google Patents

High-barrier type linear easy-to-tear nylon film and preparation method thereof Download PDF

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Publication number
CN111497405B
CN111497405B CN202010364782.2A CN202010364782A CN111497405B CN 111497405 B CN111497405 B CN 111497405B CN 202010364782 A CN202010364782 A CN 202010364782A CN 111497405 B CN111497405 B CN 111497405B
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nylon
layer
film
copolymer
tear
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CN111497405A (en
Inventor
林新土
贾露
陈曦
郑伟
刘运锦
李智尧
廖贵何
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Xiamen Changsu Industrial Co Ltd
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Xiamen Changsu Industrial 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
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/02—Open containers
    • B32B2439/06—Bags, sacks, sachets
    • 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
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    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • 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
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Abstract

The invention provides a high-barrier type linear easy-to-tear nylon film and a preparation method thereof, wherein the film layer structure of the high-barrier type linear easy-to-tear nylon film comprises a base film, a barrier evaporation layer and a surface coating; the base film is a three-layer co-extrusion biaxially oriented nylon film which is A, B, C layers from top to bottom in sequence; 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 60 to 70 percent of nylon 6 and 30 to 40 percent of special nylon composition; the special nylon composition contains MXD6-PA66 copolymer, long carbon chain nylon, nylon copolymer and compatilizer. The film has excellent oxygen barrier property, has a linear easy-tearing effect in the MD direction, and can have good linear tearing performance even if the bag is compounded with films such as PP, PE and the like.

Description

High-barrier type linear easy-to-tear nylon film and preparation method thereof
Technical Field
The invention relates to the technical field of film materials, in particular to a high-barrier type linear easy-to-tear nylon 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 mentioned in the background technology are still few in types and are difficult to meet the market demand, the invention provides a high-barrier type linear easy-to-tear nylon film, wherein the film layer structure of the high-barrier type linear easy-to-tear nylon film comprises a base film, a barrier evaporation layer and a surface coating;
the base film is a three-layer co-extrusion biaxially oriented nylon film, and 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 60 to 70 percent of nylon 6 and 30 to 40 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, the addition of special nylon MXD6 into a nylon film material is found to cause the problems of high rigidity of MXD6, easy film rupture, reduced puncture resistance and flexibility of the film, easy occurrence of pinholes in subsequent processing, obvious bow effect and low yield of the linear easy-to-tear nylon film although the linear easy-to-tear nylon film material has linear easy-to-tear property. 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 yield can be improved.
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, the coating of the evaporation blocking layer is a silicon dioxide or aluminum oxide evaporation layer; the surface coating is a hydrophobically modified polyvinyl alcohol coating.
Further, the thickness of the base film is 10-25 μm, and the thickness of the layer A and the thickness of the layer C are both 1-4 μm;
at least one surface of the A layer and the C layer is subjected to corona treatment, and the corona value is more than 50 dyn;
the thickness of the barrier evaporation layer is 10-400 nm;
the thickness of the surface coating is 0.5-2 μm.
Further, the oxygen permeability of the film is less than 0.8cc/m at 23 ℃ and 50% RH2·day·atm。
The invention also provides a preparation method of the high-barrier type linear easy-to-tear nylon film, which comprises the following steps:
step one, preparing a base film:
respectively mixing the components in the A, B, C layers in proportion, and uniformly dispersing the components by a high-speed stirrer;
melting and co-extruding the uniformly mixed raw materials through three extruders, and casting the melt to a chilled roll with the surface temperature of 15-35 ℃ through a T-shaped die to quench the cast sheet;
thirdly, humidifying the casting sheet in the second step for about 1-2 minutes in a water tank at the temperature of 40-75 ℃, drying the residual moisture on the surface of the humidified casting sheet by using an air knife, and synchronously or distributively stretching the casting sheet at the stretching temperature of 130-205 ℃ at the stretching magnification of 2.5 multiplied by 2.5-3.5 multiplied by 3.5;
fourthly, performing heat setting treatment on the film obtained in the third step 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 base film;
and step two, after the corona surface of the base film in the step one is subjected to plasma treatment, plating a layer of blocking evaporation layer, then sending the film plated with the blocking evaporation layer into coating equipment, uniformly coating a layer of hydrophobic modified polyvinyl alcohol coating on the surface of the coating, drying and rolling to obtain the high-blocking type linear easy-to-tear nylon film.
The high-barrier type linear easy-tear nylon film provided by the invention has excellent oxygen barrier property, and the oxygen transmission rate of the film is less than 0.8cc/m at 23 ℃ and 50% RH2Day atm, and has a linear easy tear effect in the MD direction, and even a bag combined with a film such as PP or PE has a good linear tear performance. Meanwhile, the transparent plastic film has the advantages of high transparency, excellent oxygen barrier property after steaming and sterilization and the like.
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 high-barrier type linear easy-to-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:
10 base film 20 barrier vapor deposition layer 30 surface coating
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 high-barrier type linear easy-to-tear nylon film provided by the embodiment of the invention comprises the following steps:
step one, preparing a base film:
respectively mixing the components in the A, B, C layers in proportion, and uniformly dispersing the components by a high-speed stirrer;
melting and co-extruding the uniformly mixed raw materials through three extruders, and casting the melt to a chilled roll with the surface temperature of 15-35 ℃ through a T-shaped die to quench the cast sheet;
thirdly, humidifying the casting sheet in the second step for about 1-2 minutes in a water tank at the temperature of 40-75 ℃, drying the residual moisture on the surface of the humidified casting sheet by using an air knife, and synchronously or distributively stretching the casting sheet at the stretching temperature of 130-205 ℃ at the stretching magnification of 2.5 multiplied by 2.5-3.5 multiplied by 3.5;
fourthly, the obtained film in the third step is subjected to heat setting treatment at the setting temperature of 180-215 ℃, at least one of the layer A and the layer C is subjected to corona treatment, and then the base film is obtained through winding and cutting;
and step two, after the corona surface of the base film in the step one is subjected to plasma treatment, plating a layer of barrier evaporation layer, then sending the film plated with the barrier evaporation layer into coating equipment, uniformly coating a layer of hydrophobic modified polyvinyl alcohol coating on the surface of the coating, and drying and rolling to obtain the high-barrier type linear easy-to-tear nylon film.
Example 1
As shown in figure 1, the high-barrier type linear easy-to-tear nylon film has a base film thickness of 15 microns, A and C layer thicknesses of 2 microns, a barrier evaporation layer thickness of 300nm, and a surface coating thickness of 0.5 micron.
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 70 percent of nylon 6 and 30 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.
the blocking evaporation layer is an aluminum oxide evaporation layer.
Example 2
As shown in figure 1, the high-barrier type linear easy-to-tear nylon film has a base film thickness of 15 microns, A and C layer thicknesses of 3 microns, a barrier evaporation layer thickness of 100nm, and a surface coating thickness of 1 micron.
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.
the blocking evaporation layer is an aluminum oxide evaporation layer.
Example 3
As shown in figure 1, the high-barrier type linear easy-to-tear nylon film has a base film thickness of 15 microns, A and C layer thicknesses of 4 microns, a barrier evaporation layer thickness of 20nm, and a surface coating thickness of 2 microns.
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 60 percent of nylon 6 and 40 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.
the barrier evaporation layer is a silicon dioxide evaporation layer.
Comparative example 1
The nylon film has a film structure comprising base film, blocking evaporating layer and surface coating. Wherein the base film is a common BOPA film, the thickness of the base film is 15 μm, the thickness of the evaporation barrier layer is 50nm, and the thickness of the surface coating is 1 μm.
The barrier evaporation layer is a silicon dioxide evaporation layer.
The preparation method comprises the following steps: and (2) carrying out plasma treatment on the surface of one side of the BOPA film, evaporating a layer of barrier evaporation layer, then sending the film plated with the barrier evaporation layer into coating equipment, uniformly coating a layer of hydrophobic modified polyvinyl alcohol coating on the surface of the coating, drying and rolling to obtain the nylon film.
Comparative example 2
A nylon film is composed of base film, barrier evaporating layer and surface coating layer. The thickness of the base film is 15 μm, the thickness of the A and C layers is 2.5 μm, the thickness of the evaporation barrier layer is 50nm, and the thickness of the surface coating is 1 μm.
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 barrier evaporation layer is a silicon dioxide evaporation layer.
The preparation method refers to the preparation method of the embodiment.
Comparative example 3
A nylon film is composed of base film, barrier evaporating layer and surface coating layer. The thickness of the base film is 15 μm, the thickness of the A and C layers is 2.5 μm, the thickness of the evaporation barrier layer is 50nm, and the thickness of the surface coating is 1 μm.
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; the B layer was composed of 70% nylon 6 and 30% MXD6/PA6 copolymer.
The barrier evaporation layer is a silicon dioxide evaporation layer.
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 a constant speed along the direction of the tear seam for 200mm, and measuring the maximum distance of the tear notch from the center line of the tear notch 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).
Oxygen transmission rate: tested according to ASTM F1927.
TABLE 1
Figure BDA0002476185230000081
Note: comparative example 1 had no linear tear and the yield rating was reported-.
As can be seen from Table 1, the films prepared in examples 1-3 of the present invention all had linear tearability in the MD direction and excellent oxygen barrier properties, and the yield evaluation was high; the films of comparative examples 2 and 3 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. The utility model provides a high resistant separates type straight line nylon film that easily tears which characterized in that: the film layer structure comprises a base film, a blocking evaporation layer and a surface coating;
the base film is a three-layer co-extrusion biaxially oriented nylon film, and 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 60 to 70 percent of nylon 6 and 30 to 40 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 high barrier type linear easy-tear nylon film according to claim 1, characterized in that: the PA66 component in the MXD6-PA66 copolymer accounts for 1-10%.
3. The high barrier type linear easy-tear nylon film according to claim 1, characterized in that: the barrier evaporation layer is a silicon dioxide or aluminum oxide evaporation layer; the surface coating is a hydrophobically modified polyvinyl alcohol coating.
4. The high barrier type linear easy-tear nylon film according to claim 1, characterized in that: the thickness of the base film is 10-25 mu m, and the thickness of the A layer and the thickness of the C layer are both 1-4 mu m;
at least one surface of the layer A and the layer C is subjected to corona treatment, and the corona value is more than 50 dyn;
the thickness of the barrier evaporation layer is 10-400 nm;
the thickness of the surface coating is 0.5-2 μm.
5. The high-barrier type linear easy-tear nylon film according to any one of claims 1 to 4, characterized in that: the oxygen permeability of the film is less than 0.8cc/m at 23 ℃ and 50% RH2·day·atm。
6. A preparation method of the high-barrier type linear easy-to-tear nylon film as claimed in any one of claims 1 to 5, is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing a base film:
respectively mixing the components in the A, B, C layers in proportion, and uniformly dispersing the components by a high-speed stirrer;
melting and co-extruding the uniformly mixed raw materials through three extruders, and casting the melt to a chilled roll with the surface temperature of 15-35 ℃ through a T-shaped die to quench the cast sheet;
thirdly, humidifying the casting sheet in the second step for 1-2 minutes in a water tank at the temperature of 40-75 ℃, drying the residual moisture on the surface of the humidified casting sheet by using an air knife, and synchronously or step-by-step stretching at the stretching temperature of 130-205 ℃ at the stretching magnification of 2.5 multiplied by 2.5-3.5 multiplied by 3.5;
fourthly, performing heat setting treatment on the film obtained in the third step 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 base film;
and step two, after the corona surface of the base film in the step one is subjected to plasma treatment, plating a layer of blocking evaporation layer, then sending the film plated with the blocking evaporation layer into coating equipment, uniformly coating a layer of hydrophobic modified polyvinyl alcohol coating on the surface of the coating, drying and rolling to obtain the high-blocking type linear easy-to-tear nylon film.
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