CN110641118B - High-barrier scratch-resistant biaxially oriented polyamide film and preparation method thereof - Google Patents

High-barrier scratch-resistant biaxially oriented polyamide film and preparation method thereof Download PDF

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CN110641118B
CN110641118B CN201910986629.0A CN201910986629A CN110641118B CN 110641118 B CN110641118 B CN 110641118B CN 201910986629 A CN201910986629 A CN 201910986629A CN 110641118 B CN110641118 B CN 110641118B
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layer
nano
barrier
nylon
modified
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CN110641118A (en
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林新土
陈曦
贾露
李智尧
刘运锦
郑伟
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
    • 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
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    • 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
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    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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    • C09D129/00—Coating compositions based on 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; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
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    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/60—Additives non-macromolecular
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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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
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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Abstract

The invention relates to the technical field of flexible packaging materials, in particular to a high-barrier scratch-resistant biaxially oriented polyamide film and a preparation method thereof. The high-barrier scratch-resistant biaxially oriented polyamide film comprises a barrier coating and a substrate layer, wherein a bottom coating is arranged between the barrier coating and the substrate layer; the substrate layer comprises A, B, C three-layer co-extrusion biaxial stretching polyamide film from top to bottom in sequence. The high-barrier scratch-resistant biaxially oriented polyamide film provided by the invention has excellent oxygen barrier property and good scratch resistance, is particularly suitable for product packaging with high barrier oxygen requirement, can further expand the application field of polyamide films, and has important practical application value.

Description

High-barrier scratch-resistant biaxially oriented polyamide film and preparation method thereof
Technical Field
The invention relates to the technical field of flexible packaging materials, in particular to a high-barrier scratch-resistant biaxially oriented polyamide film and a preparation method thereof.
Background
Polyamide films are very tough films that have the advantages of high tensile strength, high barrier properties, excellent puncture resistance, good heat and cold resistance, and the like, and are therefore widely used in many industries and fields such as food packaging, electronic packaging, pharmaceutical packaging, and the like.
With the continuous improvement of the packaging requirements of people and the continuous reduction of the addition of preservatives and the like, the requirements on the barrier performance of the film are higher and higher. However, the barrier properties of polyamide films are of moderate level in all barrier materials and still do not meet the practical requirements in some special fields with higher requirements. In addition, the processes of rolling, unreeling, slitting, transporting and the like, manual operation and the like are inevitably repeated in the manufacturing process and downstream processing application process of the polyamide film, so that damage such as scratches and scratches is easily caused, the appearance of the film is influenced, and the performance of the film is possibly influenced.
Patent CN 103350545A, published as 2013, 10, month and 16, discloses a five-layer co-extruded EVOH high-barrier nylon composite film, which has high oxygen-barrier performance, but all used EVOH resins depend on import, so that the price is high, and the integral processing difficulty of the composite film is large. The addition of a filler to nylon can improve the oxygen barrier property to a certain extent, but also has the problem that the filler is difficult to disperse in the nylon matrix.
Disclosure of Invention
In order to solve the problems mentioned in the background technology, the invention provides a high-barrier scratch-resistant biaxially oriented polyamide film, which comprises a barrier coating and a substrate layer;
a bottom coating is arranged between the barrier coating and the base material;
the substrate layer comprises A, B, C three-layer co-extrusion biaxially-oriented polyamide film from top to bottom in sequence;
the layer A and the layer C are respectively made of 37-84.5% of nylon, 10-30% of amorphous nylon, 5-30% of nano-clay modified nylon master batch and 0.5-3% of anti-sticking master batch;
the B layer comprises 40-75% of copolymer consisting of nylon 6 and nylon 66, 20-30% of MXD6 and 5-30% of nano clay modified MXD6 master batch;
the barrier coating comprises 92-98.55% of polyvinyl alcohol emulsion, 0.05-1% of dispersant, 0.5-3% of modified layered double hydroxide, 0.5-1.5% of nano silicon dioxide, 0.3-1.5% of organic microspheres and 0.1-1% of initiator.
On the basis of the technical scheme, the primer layer further comprises 10-30% of polymerizable monomer, 0.5-3% of soluble metal salt, 0.5-1% of initiator and 66-89% of solvent; the polymerizable monomer is a mixture of an acrylate monomer and acrylic acid.
Specifically, the acrylate monomer is at least one of methacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol dimethacrylate, dimethacrylate and acrylate.
Specifically, the soluble metal salt is at least one of a soluble magnesium salt, a soluble calcium salt, a soluble iron salt, a soluble zinc salt, a soluble copper salt and a soluble silver salt.
On the basis of the technical scheme, further, the thickness of the base material layer is 12-25 micrometers, the thicknesses of the layer A and the layer C are both 2-4 micrometers, and after at least one surface of the layer A and the layer C is subjected to corona treatment, the corona value of the layer A is larger than 50 dyn; the thickness of the bottom coating is 0.5-2 mu m, and the thickness of the barrier coating is 1-3 mu m.
On the basis of the technical scheme, the anti-sticking master batch is a modified nylon master batch containing an opening agent, a slipping agent and a dispersing agent.
On the basis of the technical scheme, further, the nanoclay modified nylon master batch is inorganic nanoparticle and unmodified layered hydrophilic nanoclay composite modified nylon; the nano-clay modified MXD6 master batch is a composite modified MXD6 by inorganic nano-particles and unmodified layered hydrophilic nano-clay.
On the basis of the technical scheme, the ratio of the inorganic nano particles to the unmodified layered hydrophilic nano clay is 4-5: 5-6, the total content of the inorganic nanoparticles and the unmodified layered hydrophilic nanoclay in the nanoclay modified nylon master batch is 8% -10%, and the total content of the inorganic nanoparticles and the unmodified layered hydrophilic nanoclay in the nanoclay modified MXD6 master batch is 8% -10%.
On the basis of the technical scheme, the nano-clay modified nylon master batch, the inorganic nano-particles in the nano-clay modified MXD6 master batch and the unmodified layered hydrophilic nano-clay are obtained by treating with a silane coupling agent.
On the basis of the technical scheme, specifically, the nylon is at least one of PA6, PA66, PA6/66, PA66/6, PA510, PA610, PA612, PA1010, PA1012, PA410, PA11, PA12, PA1212, MXD6, PA46, PA9T and PA 6T.
On the basis of the technical scheme, further, the inorganic nano particles are at least one of nano magnesium oxide, nano silicon dioxide and nano aluminum oxide; wherein the particle size of the inorganic nanoparticles is 30-200 nm.
On the basis of the technical scheme, the polyvinyl alcohol in the polyvinyl alcohol emulsion is modified by a silane coupling agent, the polymerization degree is 1200-3200, and the alcoholysis degree is 85-99.99%.
On the basis of the technical scheme, the modified layered double hydroxide is aliphatic carboxylic acid anion modified layered double hydroxide, wherein the layered double hydroxide is prepared by adopting a high-temperature hydrothermal method according to the mass ratio of magnesium nitrate and aluminum nitrate serving as precursors of the layered double hydroxide to magnesium nitrate and aluminum nitrate of 2-4: 1.
On the basis of the technical scheme, the organic microspheres are at least one of amino microspheres, acrylate microspheres and organic silicon microspheres.
A method for preparing a high-barrier and scratch-resistant biaxially oriented polyamide film as described in any of the above, comprising the steps of:
step 1: preparing a base material layer:
s10 preparation of nano clay modified nylon master batch
Putting the inorganic nano particles subjected to the surface treatment of the nylon and the silane coupling agent and the unmodified lamellar hydrophilic nano clay into a high-speed mixer and uniformly mixing;
and putting the mixture into a double-screw extruder, performing melt extrusion and granulation to prepare the nano-clay modified nylon master batch, wherein the temperature of the extruder is set to 230-280 ℃, the rotating speed of the extruder is 300-500 r/min, and performing dehumidification and drying for later use.
S20 preparation of nano-clay modified MXD6 master batch
Adding inorganic nano particles subjected to surface treatment by MXD6 and a silane coupling agent and unmodified layered hydrophilic nano clay into a high-speed mixer, and uniformly mixing;
and putting the mixture into a double-screw extruder for melt extrusion and granulation to prepare the nano-clay modified MXD6 master batch, wherein the temperature of the extruder is set to 230-280 ℃, the rotating speed of the extruder is 300-500 r/min, and the master batch is subjected to dehumidification and drying for later use.
S30, mixing the components in the A, B, C layers according to the proportion respectively, and dispersing the mixture uniformly by a high-speed stirrer;
s40, respectively melting and co-extruding the layers uniformly mixed in the S30 by three extruders, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 20-35 ℃ through a T-shaped die;
s50, humidifying the casting sheet in the S40 in a water tank at the temperature of 30-75 ℃ 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 the casting sheet at the stretching temperature of 130-190 ℃ at the stretching ratio of 2.5 multiplied by 2.5-3.5 multiplied by 3.5;
s60, performing heat setting on the film obtained in the step S50, performing corona treatment on at least one of the layer A and the layer C, and then rolling and cutting to obtain the base material film, wherein the thickness of the film is 12-25 mu m, and the thickness of the layer A and the thickness of the layer C are both 2-4 mu m;
step 2: uniformly coating and drying the bottom coating on the corona surface of the substrate film in the step 1 by using coating equipment, coating the prepared barrier coating liquid on the formed bottom coating through gravure, drying the coated film, and rolling to obtain the high-barrier scratch-resistant biaxially-oriented polyamide film.
The high-barrier scratch-resistant biaxially oriented polyamide film provided by the invention has the following beneficial effects:
1. the high-barrier substrate film and the coating are prepared in an organic/inorganic fusion mode, so that the high-gas-barrier performance is achieved; specifically, the inventor finds that the inorganic nanoparticles added into the nanoclay are beneficial to the dispersion of the clay in a nylon matrix, and the nanoclay and a nylon material with barrier property are made into a film, so that the dissolution coefficient of gas molecules in a polymer film is effectively reduced, a 'tortuous path' is formed, the permeation path of gas is prolonged, the diffusion of the gas in the matrix is hindered, and the gas barrier property of the nylon film is remarkably improved; meanwhile, the PVA barrier coating is arranged on the surface of the barrier nylon base material, and the layered double hydroxide and the hydrophobically modified polyvinyl alcohol can further prolong the gas permeation path, so that the permeability of the film is reduced, and the barrier property of the film is improved.
2. A large number of unsaturated residual bonds and hydroxyl groups in different bonding states on the surface of the nano silicon dioxide in the coating, and hydroxyl groups in polyvinyl alcohol, anions and metal ions in the modified layered double hydroxide, and polymeric monomers and soluble metal salts in the bottom coating can be chemically bonded or chelated, so that inorganic materials and organic polymers are synthesized into a whole to form the coating with an organic-inorganic interpenetrating network polymer structure, and the performances such as scratch resistance and the like are obviously improved while the barrier property of the film is improved; the addition of the organic microspheres can further improve the performances of the film such as scratch resistance and the like.
3. A large amount of unsaturated residual bonds and polar groups are generated after the surface of the base material is subjected to corona treatment, so that the compounding fastness of the base coating and the base material layer is improved, and the integral compounding fastness of the barrier layer and the base material layer is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic structural view of a high-barrier scratch-resistant biaxially oriented polyamide film provided by the invention.
Reference numerals:
10 barrier coating 20 base layer 30 primer layer
21A layer, 22B layer, 23C 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.
In the description of the present invention, it should be noted that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
The invention provides a high-barrier scratch-resistant biaxially oriented polyamide film, which comprises a barrier coating layer 10 and a substrate layer 20 as shown in figure 1; a bottom coating layer 30 is arranged between the barrier coating layer 10 and the base material 20; the substrate layer 20 comprises three co-extruded biaxially oriented polyamide films, namely an A layer 21, a B layer 22 and a C layer 23 from top to bottom in sequence;
the layer A and the layer C are respectively made of 37-84.5% of nylon, 10-30% of amorphous nylon, 5-30% of nano-clay modified nylon master batch and 0.5-3% of anti-sticking master batch; the B layer comprises 40-75% of copolymer consisting of nylon 6 and nylon 66, 20-30% of MXD6 and 5-30% of nano clay modified MXD6 master batch; the barrier coating comprises 92-98.55% of polyvinyl alcohol emulsion, 0.05-1% of dispersant, 0.5-3% of modified layered double hydroxide, 0.5-1.5% of nano silicon dioxide, 0.3-1.5% of organic microspheres and 0.1-1% of initiator.
The invention also provides an embodiment of a specific preparation method of the high-barrier scratch-resistant biaxially oriented polyamide film, which comprises the following steps:
step 1: preparing a base material layer:
s10 preparation of nano clay modified nylon master batch
Putting the inorganic nano particles subjected to the surface treatment of the nylon and the silane coupling agent and the unmodified lamellar hydrophilic nano clay into a high-speed mixer and uniformly mixing;
and putting the mixture into a double-screw extruder, performing melt extrusion and granulation to prepare the nano-clay modified nylon master batch, wherein the temperature of the extruder is set to 230-280 ℃, the rotating speed of the extruder is 300-500 r/min, and drying the mixture for 4 hours in a dehumidification dryer at 80 ℃ for later use.
S20 preparation of nano-clay modified MXD6 master batch
Adding inorganic nano particles subjected to surface treatment by MXD6 and a silane coupling agent and unmodified layered hydrophilic nano clay into a high-speed mixer, and uniformly mixing;
then putting the mixture into a double-screw extruder for melt extrusion and granulation to prepare the nano-clay modified MXD6 master batch, wherein the temperature of the extruder is set to 230-280 ℃, the rotating speed of the extruder is 300-500 r/min, and the mixture is dried for 4 hours in a dehumidification dryer at 80 ℃ for later use;
s30, mixing the components in the A, B, C layers according to the proportion respectively, and dispersing the mixture uniformly by a high-speed stirrer;
s40, melting and co-extruding the layers uniformly mixed in the S30 respectively through three extruders, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 25 ℃ through a T-shaped die;
s50, humidifying the casting sheet in the S40 in a 65 ℃ 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 180 ℃ at a stretching ratio of 3.0 x 3.0;
s60, carrying out heat setting on the film obtained in the step S50, carrying out corona treatment on at least one of the layer A and the layer C, and then rolling and slitting to obtain the base material film;
step 2: uniformly coating and drying the bottom coating on the corona surface of the substrate film in the step 1 by using coating equipment, coating the prepared barrier coating liquid on the formed bottom coating through gravure, drying the coated film, and rolling to obtain the high-barrier scratch-resistant biaxially-oriented polyamide film.
The invention also includes the following examples of specific high barrier, scratch resistant biaxially oriented polyamide films:
example 1
The base material layer consists of a three-layer co-extrusion two-way stretching polyamide film modified by nano clay, A, B, C layers are sequentially arranged from top to bottom, and the unwinding corona treatment is carried out on one surface of the layer A; wherein, the layer A and the layer C consist of 84.5 percent of PA6, 10 percent of amorphous nylon, 5 percent of nano clay modified nylon master batch and 0.5 percent of anti-sticking master batch; the layer B comprises 75% of copolymer consisting of nylon 6 and nylon 66, 20% of MXD6 and 5% of nano clay modified MXD6 master batch;
a bottom coating is arranged between the barrier coating and the base material;
the primer layer contains 6% of methacrylate, 5% of acrylic acid, 3% of soluble magnesium salt, 1% of initiator and 85% of solvent;
the barrier coating consists of 97.85 percent of polyvinyl alcohol emulsion, 0.05 percent of dispersant, 1 percent of modified layered double hydroxide, 0.5 percent of nano silicon dioxide, 0.4 percent of amino microspheres and 0.2 percent of initiator;
preparing a sample according to the preparation method, wherein the thickness of the base material layer is 15 micrometers, and the thicknesses of the A layer and the C layer are both 2 micrometers; the thickness of the primer layer is 1 μm; the thickness of the barrier coating was 2 μm.
Example 2
The base material layer is composed of a three-layer co-extrusion two-way stretching polyamide film modified by nano clay, A, B, C layers are sequentially arranged from top to bottom, and at least one surface of the A layer and the C layer is subjected to unreeling corona treatment; wherein the layer A and the layer C consist of 49 percent of PA6/66, 30 percent of amorphous nylon, 20 percent of nano clay modified nylon master batch and 1 percent of anti-sticking master batch; the layer B comprises 55% of copolymer consisting of nylon 6 and nylon 66, 25% of MXD6 and 20% of nano clay modified MXD6 master batch; a bottom coating is arranged between the barrier coating and the base material;
the primer layer contains 10% of polyethylene glycol diacrylate, 10% of acrylic acid, 2% of soluble calcium salt, 1% of initiator and 77% of solvent; the barrier coating is composed of 95.42% of polyvinyl alcohol emulsion, 0.08% of dispersant, 2% of modified layered double hydroxide, 1% of nano silicon dioxide, 1% of acrylate microspheres and 0.5% of initiator;
preparing a sample according to the preparation method, wherein the thickness of the base material layer is 15 micrometers, and the thicknesses of the A layer and the C layer are both 3 micrometers; the thickness of the primer layer is 1 μm; the thickness of the barrier coating was 2 μm.
Example 3
The base material layer is composed of a three-layer co-extrusion two-way stretching polyamide film modified by nano clay, A, B, C layers are sequentially arranged from top to bottom, and at least one surface of the A layer and the C layer is subjected to unreeling corona treatment; wherein the layer A and the layer C consist of 47 percent of PA66/6, 20 percent of amorphous nylon, 30 percent of nano clay modified nylon master batch and 3 percent of anti-sticking master batch; the layer B comprises 40% of copolymer consisting of nylon 6 and nylon 66, 30% of MXD6 and 30% of nano clay modified MXD6 master batch; a bottom coating is arranged between the barrier coating and the base material;
the primer layer contains 15% of triethylene glycol dimethacrylate, 15% of acrylic acid, 0.5% of soluble iron salt, 1% of an initiator and 68.5% of a solvent;
the barrier coating consists of 92% of polyvinyl alcohol emulsion, 1% of dispersant, 3% of modified layered double hydroxide, 1.5% of nano silicon dioxide, 1.5% of organic silicon microspheres and 1% of initiator;
preparing a sample according to the preparation method, wherein the thickness of the base material layer is 15 micrometers, and the thickness of the A layer and the C layer is 4 micrometers; the thickness of the primer layer is 1 μm; the thickness of the barrier coating was 2 μm.
The invention also provides the following comparative examples:
comparative example 1
The substrate layer consists of three layers of co-extrusion biaxially oriented polyamide films, A, B, C layers are sequentially arranged from top to bottom, and at least one surface of the layer A and the layer C is subjected to unreeling corona treatment; wherein layers a and C consist of 99.5% PA6 and 0.5% release masterbatch; the core layer is a copolymer consisting of 100% of nylon 6 and nylon 66;
a bottom coating is arranged between the barrier coating and the base material;
the primer layer contains 5% of polyethylene glycol diacrylate, 5% of acrylic acid, 0.5% of soluble magnesium salt, 1% of initiator and 88.5% of solvent;
the barrier coating is 100% polyvinyl alcohol emulsion.
Apart from the variables, the samples were prepared according to the preparation method described above, with a substrate layer thickness of 15 μm, in which both the A and C layers were 2 μm thick; the thickness of the primer layer is 1 μm; the thickness of the barrier coating was 2 μm.
Comparative example 2
The substrate layer consists of three layers of co-extrusion biaxially oriented polyamide films, A, B, C layers are sequentially arranged from top to bottom, and at least one surface of the layer A and the layer C is subjected to unreeling corona treatment; wherein the layer A and the layer C consist of 89 percent of PA6, 10 percent of amorphous nylon and 1 percent of anti-sticking master batch; the core layer consists of 80 percent of copolymer consisting of nylon 6 and nylon 66 and 20 percent of MXD 6;
a bottom coating is arranged between the barrier coating and the base material;
the primer layer contains 5% of polyethylene glycol diacrylate, 5% of acrylic acid, 1% of initiator and 89% of solvent;
the barrier coating is composed of 97% of polyvinyl alcohol emulsion, 1% of dispersing agent, 1% of nano silicon dioxide and 1% of initiator.
Apart from the variables, the samples were prepared according to the preparation method described above, with a substrate layer thickness of 15 μm, in which both the A and C layers were 2 μm thick; the thickness of the primer layer is 1 μm; the thickness of the barrier coating was 2 μm.
The test data for each example and comparative example is shown in table 1:
scratch resistance: placing the sample on a platform, and taking 0000# steel wool 1cm2And pressing the steel wool on a sample, pressing 200g of weight on the steel wool to enable the steel wool to rub back and forth on the surface of the sample coated with the barrier coating at a constant speed, keeping the positions of the steel wool scratched on the same sample at each time consistent as much as possible, and judging the scratch resistance according to the number (N) of times of scratching the coating. If N is less than or equal to 10, the scratch resistance is poor (marked as gamma ray)) If 10 < N < 20, the scratch resistance is normal (marked by Delta), and if N.gtoreq.20, the scratch resistance is good (marked by tangle-solidup). Oxygen transmission rate: tested according to ASTM F1927.
TABLE 1 evaluation tables of examples and comparative examples
Figure BDA0002236901780000111
As can be seen from the above table, compared with comparative examples 1 and 2, the high-barrier scratch-resistant biaxially oriented polyamide film provided by the invention has the advantages that through the matching of various technical characteristics, the prepared film has excellent oxygen barrier performance and good scratch resistance, and is particularly suitable for product packaging with high oxygen barrier and scratch resistance requirements.
Although terms such as barrier coating, substrate layer, primer layer, a layer, B layer, C layer, etc. are used more often herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention.
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 (8)

1. A high-barrier scratch-resistant biaxially oriented polyamide film is characterized in that: comprises a barrier coating and a substrate layer;
a bottom coating is arranged between the barrier coating and the base material layer;
the substrate layer is composed of A, B, C three-layer co-extruded two-way stretching polyamide films from top to bottom;
the layer A and the layer C are respectively composed of 37-84.5% of nylon, 10-30% of amorphous nylon, 5-30% of nano-clay modified nylon master batch and 0.5-3% of anti-sticking master batch;
wherein, the nylon of 37-84.5% nylon is at least one of PA6, PA6/66 and PA 66/6;
the B layer comprises 40-75% of copolymer composed of nylon 6 and nylon 66, 20-30% of MXD6 and 5-30% of nano clay modified MXD6 master batch;
the barrier coating comprises 92-98.55% of polyvinyl alcohol emulsion, 0.05-1% of dispersant, 0.5-3% of modified layered double hydroxide, 0.5-1.5% of nano silicon dioxide, 0.3-1.5% of organic microspheres and 0.1-1% of initiator;
the nano-clay modified nylon master batch is inorganic nano-particles and unmodified layered hydrophilic nano-clay composite modified nylon;
the nano-clay modified MXD6 master batch is inorganic nano-particles and unmodified layered hydrophilic nano-clay composite modified MXD 6;
the ratio of the inorganic nano particles to the unmodified layered hydrophilic nano clay is 4-5: 5-6, the total content of the inorganic nanoparticles and the unmodified layered hydrophilic nanoclay in the nanoclay modified nylon master batch is 8% -10%, and the total content of the inorganic nanoparticles and the unmodified layered hydrophilic nanoclay in the nanoclay modified MXD6 master batch is 8% -10%.
2. The high barrier, scratch resistant biaxially oriented polyamide film of claim 1, characterized in that: the bottom coating consists of 10 to 30 percent of polymerizable monomer, 0.5 to 3 percent of soluble metal salt, 0.5 to 1 percent of initiator and 66 to 89 percent of solvent;
the polymerizable monomer is a mixture of an acrylate monomer and acrylic acid.
3. The high barrier, scratch resistant biaxially oriented polyamide film of claim 1, characterized in that: the thickness of the substrate layer is 12-25 micrometers, the thicknesses of the layer A and the layer C are both 2-4 micrometers, and after at least one surface of the layer A and the layer C is subjected to corona treatment, the corona value is larger than 50 dyn;
the thickness of the bottom coating is 0.5-2 mu m, and the thickness of the barrier coating is 1-3 mu m.
4. The high barrier, scratch resistant biaxially oriented polyamide film of claim 1, characterized in that: the inorganic nano particles are at least one of nano magnesium oxide, nano silicon dioxide and nano aluminum oxide.
5. The high barrier, scratch resistant biaxially oriented polyamide film of claim 1, characterized in that: the polyvinyl alcohol in the polyvinyl alcohol emulsion is modified by a silane coupling agent, the polymerization degree is 1200-3200, and the alcoholysis degree is 85-99.99%.
6. The high barrier, scratch resistant biaxially oriented polyamide film of claim 1, characterized in that: the modified layered double hydroxide is an aliphatic carboxylic acid anion modified layered double hydroxide, wherein the layered double hydroxide is prepared by adopting a high-temperature hydrothermal method according to the mass ratio of magnesium nitrate and aluminum nitrate serving as precursors of the layered double hydroxide to magnesium nitrate and aluminum nitrate of 2-4: 1.
7. The high barrier, scratch resistant biaxially oriented polyamide film of claim 1, characterized in that: the organic microspheres are at least one of amino microspheres, acrylate microspheres and organic silicon microspheres.
8. The preparation method of the high-barrier and scratch-resistant biaxially oriented polyamide film according to any one of claims 1 to 7, characterized by comprising the following steps:
step 1: preparing a base material layer:
s10 preparation of nano clay modified nylon master batch
Putting nylon, inorganic nano particles subjected to surface treatment by a silane coupling agent and unmodified lamellar hydrophilic nano clay into a high-speed mixer, and uniformly mixing;
putting the mixture into a double-screw extruder, performing melt extrusion and granulation to prepare the nano-clay modified nylon master batch, wherein the temperature of the extruder is set to 230-280 ℃, the rotating speed of the extruder is 300-500 r/min, and performing dehumidification and drying for later use;
s20 preparation of nano-clay modified MXD6 master batch
MXD6, inorganic nano particles subjected to surface treatment by a silane coupling agent and unmodified layered hydrophilic nano clay are put into a high-speed mixer and uniformly mixed;
then putting the mixture into a double-screw extruder for melt extrusion and granulation to prepare the nano-clay modified MXD6 master batch, wherein the temperature of the extruder is set to 230-280 ℃, the rotating speed of the extruder is 300-500 r/min, and the mixture is subjected to dehumidification and drying for later use;
s30, mixing the components in the A, B, C layers according to the proportion respectively, and dispersing the mixture uniformly by a high-speed stirrer;
s40, respectively melting and co-extruding the layers uniformly mixed in the S30 by three extruders, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 20-35 ℃ through a T-shaped die;
s50, humidifying the casting sheet in the S40 in a water tank at the temperature of 30-75 ℃ 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 the casting sheet at the stretching temperature of 130-190 ℃ at the stretching ratio of 2.5 multiplied by 2.5-3.5 multiplied by 3.5;
s60, carrying out heat setting on the film obtained in the step S50, carrying out corona treatment on at least one of the layer A and the layer C, and then rolling and cutting to obtain the base material layer, wherein the thickness of the base material layer is 12-25 micrometers, and the thicknesses of the layer A and the layer C are both 2-4 micrometers;
step 2: and (2) uniformly coating and drying the bottom coating on the corona surface of the base material layer in the step (1) by using coating equipment, coating the prepared barrier coating liquid on the formed bottom coating through gravure, and then drying and rolling the coated film to obtain the high-barrier scratch-resistant biaxially-oriented polyamide film.
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