CN113370625A - Thermal shrinkage type high-barrier polyamide co-extrusion composite film and preparation method thereof - Google Patents
Thermal shrinkage type high-barrier polyamide co-extrusion composite film and preparation method thereof Download PDFInfo
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 191
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000001125 extrusion Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- 239000004417 polycarbonate Substances 0.000 claims abstract description 27
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003063 flame retardant Substances 0.000 claims abstract description 17
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 12
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- IPGANOYOHAODGA-UHFFFAOYSA-N dilithium;dimagnesium;dioxido(oxo)silane Chemical compound [Li+].[Li+].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IPGANOYOHAODGA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
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- -1 fatty acid ester Chemical class 0.000 claims description 5
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- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
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- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 3
- 235000019792 magnesium silicate Nutrition 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
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- 230000001360 synchronised effect Effects 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
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- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
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- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical compound OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 claims description 2
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
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- 239000010703 silicon Substances 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 12
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 10
- 229920006257 Heat-shrinkable film Polymers 0.000 description 8
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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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
- 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
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
- B32B2307/736—Shrinkable
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
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Abstract
The invention discloses a heat-shrinkable high-barrier polyamide co-extrusion composite film and a preparation method thereof, wherein the composite film is of a sandwich structure and is sequentially provided with a first polyamide functional layer, a polyamide barrier layer and a second polyamide functional layer from top to bottom; wherein the first polyamide functional layer and the second polyamide functional layer consist of 80-88.9% of polyamide, 10-15% of polycarbonate, 0.5-2% of liquid transparent flame retardant, 0.5-2% of antistatic agent and 0.1-1% of opening agent according to mass percentage; the polyamide barrier layer is composed of, by mass, 78-86.9% of nylon 6I, 5-10% of polycarbonate, 0.1-2% of transparent flame retardant and 5-10% of nano material. The heat-shrinkable high-barrier polyamide co-extrusion composite film provided by the invention has excellent transparency, flame retardant property, antistatic property, mechanical property, barrier property and heat-shrinkable property, is particularly suitable for the field of electronic product packaging, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of film packaging, and particularly relates to a heat-shrinkable high-barrier polyamide co-extrusion composite film and a preparation method thereof.
Background
The heat-shrinkable film is mainly characterized by being stable at normal temperature, shrinking by heating (> Tg temperature or higher), and having a shrinkage rate of 70% or more in one direction. Relative to a common film: firstly, the body is transparent, and the product image is embodied; secondly, the packing materials are tightly bound, so that the scattering resistance is good; thirdly, rain-proof, moisture-proof and mildew-proof; fourthly, the product has no recoverability and has certain anti-counterfeiting function. The heat shrinkable films in the market at present comprise PVC heat shrinkable films, PE heat shrinkable films, BOPP heat shrinkable films, BOPS heat shrinkable films, polyester heat shrinkable films and the like, and are widely applied to the markets of instant foods and beverages, electronic products, metal products and anti-counterfeiting labels.
With the advance of intelligent interconnection, the general class and the demand of electronic products are increasing, especially high-precision electronic products. The high-precision electronic product packages not only need to be externally packaged with good heat shrinkage, puncture resistance, transparency and mechanical strength, but also require the packaging film to have excellent flame retardant property, antistatic property and barrier property. For example: the barrier property is poor, and water vapor can damage electronic products in the transportation and storage processes; when the terminal is applied (such as electronic product packaging), the accumulation of static electricity is easy to break down a capacitor and a circuit board, so that electronic components are damaged; if the packaging film does not have flame retardant property, even more fire can be caused. In view of the above, a heat-shrinkable high-barrier polyamide co-extrusion composite film having superior puncture resistance, transparency and mechanical strength, and having flame retardancy, antistatic property and barrier property is in demand.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a heat-shrinkable high-barrier polyamide co-extrusion composite film and a preparation method thereof, and solves the problem that the puncture resistance, antistatic property, flame retardance and barrier property of a common heat-shrinkable film in the background art cannot meet the requirements of high-precision electronic product packaging and transportation.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the heat-shrinkable high-barrier polyamide co-extrusion composite film is of a sandwich structure and is sequentially provided with a first polyamide functional layer, a polyamide barrier layer and a second polyamide functional layer from top to bottom; wherein,
the first polyamide functional layer consists of 80-88.9% of polyamide, 10-15% of polycarbonate, 0.5-2% of liquid transparent flame retardant, 0.5-2% of antistatic agent and 0.1-1% of opening agent in percentage by mass;
the polyamide barrier layer consists of 78-86.9% of nylon 6I, 5-10% of polycarbonate, 0.1-2% of transparent flame retardant and 5-10% of nano material in percentage by mass;
the second polyamide functional layer consists of 80-88.9% of polyamide, 10-15% of polycarbonate, 0.5-2% of liquid transparent flame retardant, 0.5-2% of antistatic agent and 0.1-1% of opening agent in percentage by mass.
In a preferred embodiment of the present invention, the polyamide in the first polyamide functional layer and the second polyamide functional layer is one or a combination of nylon 6, nylon 46, nylon 56, nylon 66, nylon 11, nylon 12, nylon 1012, nylon 1212, and nylon 1313.
In a preferred embodiment of the present invention, the liquid transparent flame retardant is one or a combination of triphenyl phosphate, triethyl phosphate and trichloroethyl phosphate.
In a preferred embodiment of the present invention, the antistatic agent is one or a combination of several of ethoxylated amine, fatty acid ester, and alkyl trimethyl ammonium ethyl lactone.
In a preferred embodiment of the present invention, the opening agent is one or a combination of several of silicon dioxide, talc powder, acrylic, and silicone crosslinked microspheres.
In a preferred embodiment of the present invention, the nanomaterial is a sheet structure.
In a preferred embodiment of the present invention, the nano material is one or a combination of more of nano lithium magnesium silicate, nano sodium magnesium silicate and nano magnesium aluminum silicate.
In a preferred embodiment of the invention, the total thickness is 15-35 μm, wherein the thickness of the polyamide barrier layer is 8-25 μm.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the thermal contraction type high-barrier polyamide co-extrusion composite film is characterized by comprising the following steps:
step one, mixing the components in the first polyamide functional layer and the second polyamide functional layer in proportion, carrying out melt blending, extrusion and granulation by a double-screw extruder, and drying the obtained functional layer master batch for later use;
step two, mixing the components in the polyamide barrier layer in proportion, carrying out melt blending, extrusion and granulation by a double-screw extruder, and drying the obtained barrier layer master batch for later use;
respectively putting the functional layer master batches and the barrier layer master batches into an extruder to manufacture a first polyamide functional layer, a second polyamide functional layer and a polyamide barrier layer of the core layer; wherein the temperature of the extruder and the temperature of the T-shaped die head thereof are controlled at 220-270 ℃;
and step four, extruding and quenching the cast sheets in each layer in the step three by using a LISIM synchronous stretching method, humidifying and cleaning the surfaces of the extruded and quenched cast sheets by using a hot steaming tank at the temperature of 60-80 ℃, removing the surface steam of the cast sheets by using hot air, then performing bidirectional stretching, cooling and shaping to obtain the thermal shrinkage type high-barrier polyamide co-extrusion composite membrane.
In a preferred embodiment of the present invention, the stretching temperature in the fourth step is 160-.
Compared with the background technology, the technical scheme has the following advantages:
1. by adopting a sandwich structure design with an upper layer and a lower layer of polyamide functional layers and a core layer of a polyamide barrier layer and combining a stretching process, the surface layer film provides excellent puncture resistance and mechanical strength, and the core layer provides excellent heat shrinkage performance and barrier performance of the film;
2. the polycarbonate carbon forming capability and the ester exchange inhibition capability of the transparent flame retardant are utilized to cooperate with the flame-retardant polyamide film, so that the flame retardant property is excellent;
3. the nano material with the lamellar structure and the benzene ring structure in the nylon 6I are added in the core layer, so that the excellent barrier property of the film is provided, and the temperature and the humidity do not influence the barrier property of the film;
4. the composite film disclosed by the invention has good heat shrinkage, optical transparency, puncture resistance and mechanical properties, and simultaneously has excellent barrier property, flame retardance and antistatic property, fills the blank of a polyamide heat shrinkage film, is particularly suitable for packaging high-precision electronic products, and has broad application prospects.
Drawings
FIG. 1 is a layer structure diagram of a heat-shrinkable high-barrier polyamide co-extruded composite film.
Wherein 10-a first polyamide functional layer, 20-a polyamide barrier layer, 30-a second polyamide functional layer.
Detailed Description
The terms "upper" and "lower" are used in an orientation or positional relationship shown in the drawings only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present invention. The examples do not indicate any specific techniques or conditions, and the reagents or apparatuses used are not indicated by manufacturers in the literature of the art or by the specifications of the products, and are all conventional products commercially available.
Example 1
The heat-shrinkable high-barrier polyamide co-extrusion composite film comprises a 3-layer structure, a first polyamide functional layer 10, a polyamide barrier layer 20 and a second polyamide functional layer 30, wherein the first polyamide functional layer, the polyamide barrier layer 20 and the second polyamide functional layer are sequentially arranged from top to bottom; the first polyamide functional layer 10 and the second polyamide functional layer 30 are 5 μm thick, and the components of the first polyamide functional layer 10 and the second polyamide functional layer comprise PA 685.5%, polycarbonate 12%, triphenyl phosphate 1%, ethoxylated amine 1% and silica 0.5% by mass percentage; the thickness of the polyamide barrier layer 20 is 15 μm, and the components of the polyamide barrier layer comprise, by mass, PA6I 83%, polycarbonate 8%, triphenyl phosphate 1% and nano lithium magnesium silicate 8%.
Example 2
The heat-shrinkable high-barrier polyamide co-extrusion composite film comprises a 3-layer structure, a first polyamide functional layer 10, a polyamide barrier layer 20 and a second polyamide functional layer 30, wherein the first polyamide functional layer, the polyamide barrier layer 20 and the second polyamide functional layer are sequentially arranged from top to bottom; the first polyamide functional layer 10 and the second polyamide functional layer 30 are 5 microns thick, and the components of the first polyamide functional layer and the second polyamide functional layer comprise, by mass, PA 680%, polycarbonate 15%, triphenyl phosphate 2%, ethoxylated amine 2% and silica 1%; the thickness of the polyamide barrier layer 20 is 15 μm, and the components of the polyamide barrier layer comprise, by mass, PA6I 78%, polycarbonate 10%, triphenyl phosphate 2% and nano lithium magnesium silicate 10%.
Example 3
The heat-shrinkable high-barrier polyamide co-extrusion composite film comprises a 3-layer structure, a first polyamide functional layer 10, a polyamide barrier layer 20 and a second polyamide functional layer 30, wherein the first polyamide functional layer, the polyamide barrier layer 20 and the second polyamide functional layer are sequentially arranged from top to bottom; wherein, the thickness of the first and second polyamide functional layers 10, 30 is 5 μm, and the components thereof comprise PA 688.9%, polycarbonate 10%, triphenyl phosphate 0.5%, ethoxylated amine 0.5% and silica 0.1% by mass percentage; the polyamide barrier layer 20 is 15 μm thick and comprises, by mass, PA6I 86.9.9%, polycarbonate 8%, triphenyl phosphate 0.1%, and nano lithium magnesium silicate 5%.
Example 4
The heat-shrinkable high-barrier polyamide co-extrusion composite film comprises a 3-layer structure, a first polyamide functional layer 10, a polyamide barrier layer 20 and a second polyamide functional layer 30, wherein the first polyamide functional layer, the polyamide barrier layer 20 and the second polyamide functional layer are sequentially arranged from top to bottom; the first polyamide functional layer 10 and the second polyamide functional layer 30 are 5 microns thick, and the components of the first polyamide functional layer and the second polyamide functional layer comprise PA 5685.5%, polycarbonate 12%, triethyl phosphate 1%, fatty acid ester 1% and acrylic acid 0.5% in percentage by mass; the thickness of the polyamide barrier layer 20 is 15 μm, and the components of the polyamide barrier layer comprise, by mass, PA6I 83%, polycarbonate 8%, triethyl phosphate 1% and nano magnesium silicate sodium 8%.
Comparative example 1
A commercial 25 μm biaxially oriented nylon 6 film.
Comparative example 2
A 25-micron biaxially oriented nylon 6 film is manufactured.
Comparative example 3
A 25-micron biaxially oriented nylon 6I film is prepared.
Comparative example 4
The heat-shrinkable high-barrier polyamide co-extrusion composite film comprises a 3-layer structure, a first polyamide functional layer 10, a polyamide barrier layer 20 and a second polyamide functional layer 30, wherein the first polyamide functional layer, the polyamide barrier layer 20 and the second polyamide functional layer are sequentially arranged from top to bottom; the first polyamide functional layer 10 and the second polyamide functional layer 30 are 5 μm thick, and comprise the components of PA 695%, triphenyl phosphate 2%, ethoxylated amine 2% and silicon dioxide 1% by mass percent; the thickness of the polyamide barrier layer 20 is 15 μm, and the components of the polyamide barrier layer comprise PA6I 88%, triphenyl phosphate 2% and nano lithium magnesium silicate 10% by mass percentage.
Comparative example 5
The heat-shrinkable high-barrier polyamide co-extrusion composite film comprises a 3-layer structure, a first polyamide functional layer 10, a polyamide barrier layer 20 and a second polyamide functional layer 30, wherein the first polyamide functional layer, the polyamide barrier layer 20 and the second polyamide functional layer are sequentially arranged from top to bottom; wherein, the thickness of the first and second polyamide functional layers 10, 30 is 5 μm, and the components thereof comprise PA 686.5%, polycarbonate 12%, ethoxylated amine 1% and silicon dioxide 0.5% by mass percentage; the thickness of the polyamide barrier layer 20 is 15 μm, and the components of the polyamide barrier layer comprise PA6I 84%, polycarbonate 8% and nano lithium magnesium silicate 8% by mass percentage.
Comparative example 6
The heat-shrinkable high-barrier polyamide co-extrusion composite film comprises a 3-layer structure, a first polyamide functional layer 10, a polyamide barrier layer 20 and a second polyamide functional layer 30, wherein the first polyamide functional layer, the polyamide barrier layer 20 and the second polyamide functional layer are sequentially arranged from top to bottom; wherein, the thickness of the first and second polyamide functional layers 10, 30 is 5 μm, and the components thereof comprise PA 686.5%, polycarbonate 12%, triphenyl phosphate 1% and silicon dioxide 0.5% by mass percentage; the polyamide barrier layer 20 is 15 μm thick and comprises, by mass, PA6I 83%, polycarbonate 8%, triphenyl phosphate 1%, and nano lithium magnesium silicate 8%.
Comparative example 7
The heat-shrinkable high-barrier polyamide co-extrusion composite film comprises a 3-layer structure, a first polyamide functional layer 10, a polyamide barrier layer 20 and a second polyamide functional layer 30, wherein the first polyamide functional layer, the polyamide barrier layer 20 and the second polyamide functional layer are sequentially arranged from top to bottom; the first polyamide functional layer 10 and the second polyamide functional layer 30 are 5 μm thick, and the components of the first polyamide functional layer 10 and the second polyamide functional layer comprise PA 685.5%, polycarbonate 12%, triphenyl phosphate 1%, ethoxylated amine 1% and silica 0.5% by mass percentage; the thickness of the polyamide barrier layer 20 is 15 μm, and the components of the polyamide barrier layer comprise PA6I 91%, polycarbonate 8% and triphenyl phosphate 1% by mass percentage.
Comparative example 8
The heat-shrinkable high-barrier polyamide co-extrusion composite film comprises a 3-layer structure, a first polyamide functional layer 10, a polyamide barrier layer 20 and a second polyamide functional layer 30, wherein the first polyamide functional layer, the polyamide barrier layer 20 and the second polyamide functional layer are sequentially arranged from top to bottom; wherein, the thickness of the first and second polyamide functional layers 10, 30 is 5 μm, and the components thereof comprise PA 658%, polycarbonate 30%, triphenyl phosphate 5%, ethoxylated amine 5% and silicon dioxide 2% by mass percentage; the polyamide barrier layer 20 is 15 μm thick and comprises, by mass, PA6I 50%, polycarbonate 30%, triphenyl phosphate 5%, and nano lithium magnesium silicate 15%.
Comparative example 9
The heat-shrinkable high-barrier polyamide co-extrusion composite film comprises a 3-layer structure, a first polyamide functional layer 10, a polyamide barrier layer 20 and a second polyamide functional layer 30, wherein the first polyamide functional layer, the polyamide barrier layer 20 and the second polyamide functional layer are sequentially arranged from top to bottom; the first polyamide functional layer 10 and the second polyamide functional layer 30 are 5 μm thick, and the components of the first polyamide functional layer 10 and the second polyamide functional layer comprise PA 694.7%, polycarbonate 5%, triphenyl phosphate 0.1%, ethoxylated amine 0.1% and silica 0.1% by mass percentage; the thickness of the polyamide barrier layer 20 is 15 μm, and the components of the polyamide barrier layer comprise, by mass, PA6I 92.9.9%, polycarbonate 5%, triphenyl phosphate 0.1%, and nano lithium magnesium silicate 2%.
The above examples 1 to 4 and comparative examples 4 to 9 were prepared by the method for preparing a heat-shrinkable high-barrier polyamide co-extruded composite film according to the present invention, wherein the method comprises the following steps:
step one, mixing the components in the polyamide functional layer in proportion, carrying out melt blending, extrusion and granulation by a double-screw extruder, and drying the obtained functional layer master batch for later use;
step two, mixing the components in the polyamide barrier layer in proportion, carrying out melt blending, extrusion and granulation by a double-screw extruder, and drying the obtained barrier layer master batch for later use;
step three: putting the master batch obtained in the step one into a 10-layer extruder and a 30-layer extruder to prepare 10 layers and 30 layers; putting the master batch obtained in the step two into a 20-layer extruder to prepare 20 layers; wherein the temperature of each extruder and the temperature of the T-shaped die head thereof are controlled at 220-270 ℃;
and step four, extruding and quenching the cast sheets in the steps three by using a LISIM synchronous stretching method, humidifying and cleaning the surfaces of the extruded and quenched cast sheets by using a 60-80 ℃ hot steaming tank, removing the evaporation on the surfaces of the cast sheets by using hot air, then performing bidirectional stretching (the stretching temperature is 160-190 ℃, the stretching multiplying factor is 0.5-3.8), and cooling and shaping to obtain the heat-shrinkable high-barrier polyamide co-extruded composite membrane.
The films prepared in the examples and comparative examples were subjected to performance tests, and the test evaluation results are shown in table 1:
TABLE 1
As can be seen from examples 1-4 and comparative examples 1-9 in Table 1, the heat-shrinkable high-barrier polyamide co-extruded composite film of the examples has excellent heat-shrinkable performance, transparency, flame retardant performance, antistatic performance, mechanical properties, barrier performance and good comprehensive performance.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; 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 (10)
1. A thermal contraction type high-barrier polyamide co-extrusion composite film is characterized in that: the polyamide composite material is sequentially provided with a first polyamide functional layer, a polyamide barrier layer and a second polyamide functional layer from top to bottom; wherein,
the first polyamide functional layer consists of 80-88.9% of polyamide, 10-15% of polycarbonate, 0.5-2% of liquid transparent flame retardant, 0.5-2% of antistatic agent and 0.1-1% of opening agent in percentage by mass;
the polyamide barrier layer consists of 78-86.9% of nylon 6I, 5-10% of polycarbonate, 0.1-2% of transparent flame retardant and 5-10% of nano material in percentage by mass;
the second polyamide functional layer consists of 80-88.9% of polyamide, 10-15% of polycarbonate, 0.5-2% of liquid transparent flame retardant, 0.5-2% of antistatic agent and 0.1-1% of opening agent in percentage by mass.
2. The heat-shrinkable high-barrier polyamide co-extruded composite film according to claim 1, wherein: the polyamide in the first polyamide functional layer and the second polyamide functional layer is one or a combination of more of nylon 6, nylon 46, nylon 56, nylon 66, nylon 11, nylon 12, nylon 1012, nylon 1212 and nylon 1313.
3. The heat-shrinkable high-barrier polyamide co-extruded composite film according to claim 1, wherein: the liquid transparent flame retardant is one or a combination of more of triphenyl phosphate, triethyl phosphate and trichloroethyl phosphate.
4. The heat-shrinkable high-barrier polyamide co-extruded composite film according to claim 1, wherein: the antistatic agent is one or a combination of more of ethoxylated amine, fatty acid ester and alkyl trimethyl ammonium ethyl lactone.
5. The heat-shrinkable high-barrier polyamide co-extruded composite film according to claim 1, wherein: the opening agent is one or a combination of silicon dioxide, talcum powder, acrylic and organic silicon crosslinked microspheres.
6. The heat-shrinkable high-barrier polyamide co-extruded composite film according to claim 1, wherein: the nano material is in a lamellar structure.
7. The heat-shrinkable high-barrier polyamide co-extruded composite film according to claim 1, wherein: the nano material is one or a combination of more of nano lithium magnesium silicate, nano sodium magnesium silicate and nano magnesium aluminum silicate.
8. The heat-shrinkable high-barrier polyamide co-extruded composite film according to claim 1, wherein: the total thickness is 15-35 μm, wherein the thickness of the polyamide barrier layer is 8-25 μm.
9. The preparation method of the heat-shrinkable high-barrier polyamide co-extruded composite film as claimed in any one of claims 1 to 8, wherein the method comprises the following steps:
step one, mixing the components in the first polyamide functional layer and the second polyamide functional layer in proportion, carrying out melt blending, extrusion and granulation by a double-screw extruder, and drying the obtained functional layer master batch for later use;
step two, mixing the components in the polyamide barrier layer in proportion, carrying out melt blending, extrusion and granulation by a double-screw extruder, and drying the obtained barrier layer master batch for later use;
respectively putting the functional layer master batches and the barrier layer master batches into an extruder to manufacture a first polyamide functional layer, a second polyamide functional layer and a polyamide barrier layer of the core layer; wherein the temperature of the extruder and the temperature of the T-shaped die head thereof are controlled at 220-270 ℃;
and step four, extruding and quenching the cast sheets in each layer in the step three by using a LISIM synchronous stretching method, humidifying and cleaning the surfaces of the extruded and quenched cast sheets by using a hot steaming tank at the temperature of 60-80 ℃, removing the surface steam of the cast sheets by using hot air, then performing bidirectional stretching, cooling and shaping to obtain the thermal shrinkage type high-barrier polyamide co-extrusion composite membrane.
10. The preparation method of the heat-shrinkable high-barrier polyamide co-extrusion composite film according to claim 9, wherein the preparation method comprises the following steps: the stretching temperature in the fourth step is 160-190 ℃, and the stretching ratio is 0.5-3.8.
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| CN114055891A (en) * | 2021-10-26 | 2022-02-18 | 厦门长塑实业有限公司 | Heat-shrinkable polyamide film and preparation method and application thereof |
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