CN110435267A - A kind of polyamide film and preparation method thereof suitable for electronic product outer packing - Google Patents

A kind of polyamide film and preparation method thereof suitable for electronic product outer packing Download PDF

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Publication number
CN110435267A
CN110435267A CN201910723220.XA CN201910723220A CN110435267A CN 110435267 A CN110435267 A CN 110435267A CN 201910723220 A CN201910723220 A CN 201910723220A CN 110435267 A CN110435267 A CN 110435267A
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Prior art keywords
nylon
polyphenylene sulfide
polyamide film
layer
electronic product
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CN201910723220.XA
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CN110435267B (en
Inventor
林新土
牟青英
刘运锦
陈曦
贾露
郑伟
刘跃军
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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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • 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
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/5825—Tear resistant
    • 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
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor 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
    • B32B2435/00—Closures, end caps, stoppers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to flexible packing material technical field, in particular to a kind of polyamide film and preparation method thereof suitable for electronic product outer packing, wherein the polyamide film is 3-tier architecture, is followed successively by upper epidermis, sandwich layer, layer；The upper epidermis and layer include following preparing raw material: polyphenylene sulfide, nylon, toughener, compatilizer, heat stabilizer, inorganic particulate, slipping agent, opening agent；The sandwich layer includes following preparing raw material: copolymer nylon, MXD6-PA66 copolymer, polyphenylene sulfide, modified polyphenyl thioether, compatilizer, heat stabilizer.Have the characteristics that excellent heat resistance, chemical-resistance, dimensional stability, low water absorbable, flame retardant property, barrier property and toughness using polyamide film prepared by the present invention, can be widely applied to the fields such as electronic product.

Description

A kind of polyamide film and preparation method thereof suitable for electronic product outer packing
Technical field
The present invention relates to flexible packing material technical field, in particular to a kind of polyamide suitable for electronic product outer packing Film and preparation method thereof.
Background technique
With the development of scientific and technological progress and society, people to the exploitation of new technology and new material, using more and more extensive, it is right Electronics, the requirement of electrical apparatus insulation material are higher and higher, especially the electrically insulating material with high heat resistance, hydrolytic resistance, together When there is the new material of low water absorbable and low-hygroscopicity again.
Tensile strength is big, barrier property is high, impact resistant strength is big, heat-resisting cold resistance is good, electrical isolation because having for polyamide film The good characteristics such as excellent performance, and numerous industries and the field such as be widely used in food packaging, electronic packaging, medical packaging.
But there is also following problems for polyamide film: the not high and low dimensional stability of heat resistance, hygroscopic, moisture absorption and resistance Combustion property is poor；Since the defect of this respect exists, limits polyamide film and packed in the application in some fields, such as electronic product Deng.
And PPS films have excellent chemical corrosion resistance, heat resistance, while also having fire-retardant, insulation, good Mechanical property and dimensional stability and be concerned.
In recent years, high-performance polyphenylene sulfide film obtains relatively broad application, especially in some pairs of environmental condition requirements It is relatively high, such as the environment of wet environment and the perishable environment or even electron radiation of chemicals, while as electronic seal Material is applied to electronic component, can be also used for the sealing material of mechanical seal, many researchers are dedicated to polyphenylene sulfide thus The research of ether film.
PPS films have excellent heat resistance, and anti-flammability, rigidity, chemical-resistant reagent, electrical insulating property be excellent, moisture absorption Property it is low the features such as, meanwhile, also have lower dielectric constant, under hot and humid environment have excellent insulating properties；It is especially suitable It shares in electric appliance and electronic instrument, mechanical part, automobile component etc..
Therefore, it is combined with polyamide, is expected to prepare a kind of electrical isolation material with high heat resistance, fire-retardant Material, while solving the problems, such as that polyamide film exists with the new thin-film material of low water absorbable and low-hygroscopicity again, it realizes in electricity The application in the fields such as sub- product packaging.
Summary of the invention
To solve the problems in above-mentioned background technique, the present invention provides a kind of polyamide suitable for electronic product outer packing Film, the polyamide film are 3-tier architecture, are followed successively by upper epidermis, sandwich layer, layer；
Wherein, the upper epidermis and layer include following preparing raw material: polyphenylene sulfide, nylon, toughener, compatible Agent, heat stabilizer, inorganic particulate, slipping agent, opening agent；
The sandwich layer includes following preparing raw material: copolymer nylon, MXD6-PA66 copolymer, polyphenylene sulfide, modified polyphenyl sulphur Ether, compatilizer, heat stabilizer.
On the basis of above scheme, it is preferable that the upper epidermis and layer include the raw material of following mass fraction:
The sandwich layer includes the raw material of following mass fraction:
On the basis of above scheme, it is preferable that the copolymer nylon is nylon 6/66, nylon66 fiber/6, nylon 6/10, Buddhist nun Imperial 66/6T, nylon 6I/6T, nylon 6/6I, nylon 1010/6, nylon 10T/11, nylon 1010/66, nylon66 fiber/610, nylon 1010/66/610, nylon 6/66/610, nylon 6/611, nylon 6/66/12, nylon66 fiber/6I, one of nylon66 fiber/6T/6I Or it is a variety of.
On the basis of above scheme, it is preferable that the toughener be thermoplastic elastomer (TPE), polyamide-based elastomer, One of copolymer nylon is a variety of.
On the basis of above scheme, it is preferable that the compatilizer is glycidyl methacrylate graft benzene second Alkenes elastomer, epoxy resin, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer and acrylic acid-grafted poly- One of diphenyl sulfide is a variety of.
On the basis of above scheme, it is preferable that the inorganic particulate is through Silane coupling agent KH550 treated carbon Sour magnesium, aluminium oxide, calcium carbonate, diatomite, talcum powder, barium sulfate, kaolinite, titanium dioxide, wollastonite, one in silica Kind is a variety of.
On the basis of above scheme, it is preferable that the slipping agent is that erucyl amide, oleamide, ethylenebis are hard One of acyl amine, silicone powder, silicone oil, polyethylene wax, oxidized polyethylene wax are a variety of.
On the basis of above scheme, it is preferable that the opening agent is fumed silica or precipitation method dioxy SiClx.
On the basis of above scheme, it is preferable that the polyphenylene sulfide is linear polyphenylene sulfide.
On the basis of above scheme, it is preferable that the modified polyphenyl thioether is organosilicon grafted and modified polyphenylene sulfide, more One of end group polyhedral silsesquioxane graft modification polyphenylene sulfide, graphene in-situ polymerization modified polyphenyl thioether are more Kind.
On the basis of above scheme, it is preferable that the melt flow rate (MFR) of polyphenylene sulfide in the upper epidermis and layer For 30~100g/10min, fusing point is 265~290 DEG C；Polyphenylene sulfide in the sandwich layer is copolymerized polyphenylene sulfide, and fusing point is 240~265 DEG C.
On the basis of above scheme, it is preferable that the nylon is nylon 6, nylon 46, nylon 56, nylon 510, nylon 66, MXD6, nylon 69, nylon 610, nylon 611, nylon 612, Nylon 1012, nylon 11, nylon 12, nylon 1212, nylon 6T, nylon 6I/6T, the copolymer of nylon 6 and nylon66 fiber, nylon 9 T, nylon 10T, one of nylon 12T or a variety of.
On the basis of above scheme, it is preferable that the heat stabilizer is higher alcohols phosphoric acid ester sodium, castor oil phosphate ester One or both of salt, mantoquita heat stabilizer.
On the basis of above scheme, it is preferable that the dispersion particle diameter of nylon in the base in the upper epidermis and layer For 10~400nm.
On the basis of above scheme, it is preferable that the inorganic particulate partial size is 0.01~4 μm.
On the basis of above scheme, it is preferable that the skin depth is 1.5~6 μm, the polyamide film thickness It is 10~30 μm.
The present invention also provides a kind of preparation methods of polyamide film suitable for electronic product outer packing, including following step It is rapid:
Step 1: each component in upper epidermis, sandwich layer and layer is mixed respectively, and it is stirred, the stirring It is stirred and is uniformly dispersed preferably by high-speed mixer；
Step 2: by the raw material of upper epidermis, sandwich layer and layer respectively by respective extruder melting extrusion, by T The outflow of pattern head, and it is cooling in chilling roller, form non-stretched sheet material；
Step 3: non-stretched sheet material to be carried out to substep or synchro-draw at 60~140 DEG C, film, the stretching are obtained Multiplying power is preferably 2.6*2.6~3.5*3.5；
Step 4: the film after stretching is carried out thermal finalization at 150~210 DEG C, the setting time is preferably 5~ 20s, relaxation rate are preferably 3%, and carry out sided corona treatment at least one surface of film, are then wound, and are finally obtained described Polyamide film, the polyamide film thickness is preferably 10~30 μm.
A kind of polyamide film suitable for electronic product outer packing provided by the invention and preparation method thereof with it is existing Technology is compared, have following technical principle and the utility model has the advantages that
1, it can be mentioned in the present invention by adding thermoplastic nylon material, toughener and inorganic particulate in polyphenylene sulfide Its high toughness and intensity；Meanwhile by adding compatilizer, can improve between nylon material and inorganic particulate and matrix polyphenylene sulfide Interface binding power, when being prepared into film surface layer, its excellent heat resistance, anti-flammability and low water absorbable can be given full play to； Nylon material and compatilizer are added in the base, and the compatibility and caking property of surface layer and sandwich layer can be improved；Using slipping agent and Opening agent can be improved the smoothness of film surface and reduce the caking property between film, improves the winding performance of film.
2, sandwich layer uses copolymer nylon and compatilizer, and the compatibility of copolymer nylon and polyphenylene sulfide can be improved, and improves thin Flexibility, puncture resistance and the sandwich layer of film and the compatibility and caking property on surface layer；Modified polyphenyl thioether is added, with polyphenyl Thioether compatibility is good, and can be further improved anti-flammability；The addition of MXD6-PA66 copolymer can be heat-resisting in raising film On the basis of performance, dimensional stability, and assign the barrier properties for gases such as the excellent oxygen of film and extremely low water absorption rate.
3, there is excellent heat resistance, chemical-resistance, dimensional stability, low using the polyamide film of this method preparation The features such as water imbibition, flame retardant property, barrier property and toughness, can be widely applied to the fields such as electronic product.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is this hair Bright some embodiments for those of ordinary skill in the art without any creative labor, can be with It obtains other drawings based on these drawings.
Fig. 1 is a kind of structural schematic diagram of the polyamide film suitable for electronic product outer packing provided by the invention.
Appended drawing reference:
100 upper epidermis, 200 sandwich layer, 300 layer
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art Every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that term " center ", " longitudinal direction ", " transverse direction ", "upper", "lower", The orientation or positional relationship of the instructions such as "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outside" is It is based on the orientation or positional relationship shown in the drawings, is merely for convenience of description of the present invention and simplification of the description, rather than instruction or dark Show that signified device or element must have a particular orientation, be constructed and operated in a specific orientation, therefore should not be understood as pair Limitation of the invention.In addition, term " first ", " second " are used for description purposes only, it is not understood to indicate or imply opposite Importance.
The present invention provides a kind of polyamide film suitable for electronic product outer packing, as shown in Figure 1, the polyamide is thin Film is 3-tier architecture, is followed successively by upper epidermis 100, sandwich layer 200, layer 300.
Wherein, the upper epidermis and layer include following preparing raw material: polyphenylene sulfide, nylon, toughener, compatible Agent, heat stabilizer, inorganic particulate, slipping agent, opening agent；
The sandwich layer includes following preparing raw material: copolymer nylon, MXD6-PA66 copolymer, polyphenylene sulfide, modified polyphenyl sulphur Ether, compatilizer, heat stabilizer.
On the basis of above scheme, it is preferable that the upper epidermis and layer include the raw material of following mass fraction:
On the basis of above scheme, it is preferable that the sandwich layer includes the raw material of following mass fraction:
On the basis of above scheme, it is preferable that the copolymer nylon is nylon 6/66, nylon66 fiber/6, nylon 6/10, Buddhist nun Imperial 66/6T, nylon 6I/6T, nylon 6/6I, nylon 1010/6, nylon 10T/11, nylon 1010/66, nylon66 fiber/610, nylon 1010/66/610, nylon 6/66/610, nylon 6/611, nylon 6/66/12, nylon66 fiber/6I, one of nylon66 fiber/6T/6I Or it is a variety of.
On the basis of above scheme, it is preferable that the toughener be thermoplastic elastomer (TPE), polyamide-based elastomer, One of copolymer nylon is a variety of.
On the basis of above scheme, it is preferable that the compatilizer is glycidyl methacrylate graft benzene second Alkenes elastomer, epoxy resin, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer and acrylic acid-grafted poly- One of diphenyl sulfide is a variety of.
On the basis of above scheme, it is preferable that the inorganic particulate is through Silane coupling agent KH550 treated carbon Sour magnesium, aluminium oxide, calcium carbonate, diatomite, talcum powder, barium sulfate, kaolinite, titanium dioxide, wollastonite, one in silica Kind is a variety of.
On the basis of above scheme, it is preferable that the slipping agent is that erucyl amide, oleamide, ethylenebis are hard One of acyl amine, silicone powder, silicone oil, polyethylene wax, oxidized polyethylene wax are a variety of.
On the basis of above scheme, it is preferable that the opening agent is fumed silica or precipitation method dioxy SiClx.
On the basis of above scheme, it is preferable that the polyphenylene sulfide is linear polyphenylene sulfide.
On the basis of above scheme, it is preferable that the modified polyphenyl thioether is organosilicon grafted and modified polyphenylene sulfide, more At least one of end group polyhedral silsesquioxane graft modification polyphenylene sulfide, graphene in-situ polymerization modified polyphenyl thioether.
On the basis of above scheme, it is preferable that the melt flow rate (MFR) of polyphenylene sulfide in the upper epidermis and layer For 30~100g/10min, fusing point is 265~290 DEG C；Polyphenylene sulfide in the sandwich layer is copolymerized polyphenylene sulfide, and fusing point is 240~265 DEG C.
On the basis of above scheme, it is preferable that the nylon is nylon 6, nylon 46, nylon 56, nylon 510, nylon 66, MXD6, nylon 69, nylon 610, nylon 611, nylon 612, Nylon 1012, nylon 11, nylon 12, nylon 1212, nylon 6T, nylon 6I/6T, the copolymer of nylon 6 and nylon66 fiber, nylon 9 T, nylon 10T, one of nylon 12T or a variety of.
On the basis of above scheme, it is preferable that the heat stabilizer is higher alcohols phosphoric acid ester sodium, castor oil phosphate ester One of salt, mantoquita heat stabilizer are a variety of.
On the basis of above scheme, it is preferable that the dispersion particle diameter of nylon in the base in the upper epidermis and layer For 10~400nm.
On the basis of above scheme, it is preferable that the inorganic particulate partial size is 0.01~4 μm.
On the basis of above scheme, it is preferable that the skin depth is 1.5~6 μm, the polyamide film thickness It is 10~30 μm.
The present invention also provides a kind of preparation methods of polyamide film suitable for electronic product outer packing, including following step It is rapid:
Step 1: each component in upper epidermis, sandwich layer and layer is mixed respectively, and it is stirred, the stirring It is stirred and is uniformly dispersed preferably by high-speed mixer；
Step 2: by the raw material of upper epidermis, sandwich layer and layer respectively by respective extruder melting extrusion, by T The outflow of pattern head, and it is cooling in chilling roller, form non-stretched sheet material；
Step 3: non-stretched sheet material to be carried out to substep or synchro-draw at 60~140 DEG C, film, the stretching are obtained Multiplying power is preferably 2.6*2.6~3.5*3.5；
Step 4: the film after stretching is carried out thermal finalization at 150~210 DEG C, the setting time is preferably 5~ 20s, relaxation rate are preferably 3%, and carry out sided corona treatment at least one surface of film, are then wound, and are finally obtained described Polyamide film, the polyamide film thickness is preferably 10~30 μm.
The present invention also provides embodiments as described below:
Embodiment 1
The composition of upper epidermis are as follows: the mass percentage content of polyphenylene sulfide is 65.6%, the mass percentage content of nylon 6 It is 20%, the mass percentage content of thermoplastic elastomer (TPE) is 8%, glycidyl methacrylate graft phenylethylene elasticity The mass percentage content of body is 5%, and the mass percentage content of higher alcohols phosphoric acid ester sodium is 0.2%, the quality of magnesium carbonate Degree is 0.5%, and the mass percentage content of erucyl amide is 0.2%, and fumed silica mass percent contains Amount is 0.5%.
The composition of sandwich layer are as follows: the mass percentage content of copolymer nylon 6/66 is the matter of 61.9%, MXD6-PA66 copolymer Measuring degree is 10%, and the mass percentage content of polyphenylene sulfide is 5%, the quality of organosilicon grafted and modified polyphenylene sulfide Degree is 20%, and the mass percentage content of epoxy resin is 3%, the mass percentage content of Castor Oil Phosphate Ester Salt It is 0.1%.
The composition of layer are as follows: the mass percentage content of polyphenylene sulfide is 78%, the mass percentage content of nylon 510 It is 12%, the mass percentage content of thermoplastic elastomer (TPE) is 5%, and the mass percentage content of acrylic acid-grafted polyphenylene sulfide is 3%, the mass percentage content of higher alcohols phosphoric acid ester sodium is 0.2%, and the mass percentage content of talcum powder is 1%, oleic acid The mass percentage content of amide is 0.3%, and fumed silica mass percentage content is 0.5%.
Wherein, upper epidermis with a thickness of 1.5 μm；Sandwich layer with a thickness of 12 μm；Layer with a thickness of 1.5 μm.
According to the component of above layers structure, it is prepared according to aforementioned preparation process.
Embodiment 2
The composition of upper epidermis are as follows: the mass percentage content of polyphenylene sulfide is 75.8%, and the mass percent of nylon 610 contains Amount is 15%, and the mass percentage content of polyamide-based elastomer is 3%, glycidyl methacrylate graft phenylethylene The mass percentage content of elastomer is 4%, and the mass percentage content of Castor Oil Phosphate Ester Salt is 0.5%, the matter of diatomite Measuring degree is 1%, and the mass percentage content of ethylenebisstearamide is 0.2%, precipitated silica quality Degree is 0.5%.
The composition of sandwich layer are as follows: the mass percentage content of copolymer nylon 66/6 is the matter of 45.9%, MXD6-PA66 copolymer Measuring degree is 25%, and the mass percentage content of polyphenylene sulfide is 10%, the grafting of multiterminal polyhedral silsesquioxane The mass percentage content of modified polyphenyl thioether is 15%, and the mass percentage content of acrylic acid-grafted polyphenylene sulfide is 4%, copper The mass percentage content of salt heat stabilizer is 0.1%.
The composition of layer are as follows: the mass percentage content of polyphenylene sulfide is 75.5%, and the mass percent of nylon 12 contains Amount is 12%, and the mass percentage content of copolymer nylon is 5%, and Ethylene-butyl acrylate-glycidyl methacrylate is total The mass percentage content of polymers is 5%, and the mass percentage content of higher alcohols phosphoric acid ester sodium is 0.2%, the matter of aluminium oxide Measuring degree is 1.5%, and the mass percentage content of erucyl amide is 0.3%, fumed silica mass percent Content is 0.5%.
Wherein, upper epidermis with a thickness of 2 μm；Sandwich layer with a thickness of 10 μm, layer with a thickness of 3 μm.
According to the component of above layers structure, it is prepared according to aforementioned preparation process.
Embodiment 3
The composition of upper epidermis are as follows: the mass percentage content of polyphenylene sulfide is 81.6%, and the mass percent of nylon 11 contains Amount is 10%, and the mass percentage content of copolymer nylon is 4%, and the mass percentage content of epoxy resin is 3%, and mantoquita heat is steady The mass percentage content for determining agent is 0.2%, and the mass percentage content of barium sulfate is 0.5%, the quality percentage of polyethylene wax It is 0.2% than content, precipitated silica mass percentage content is 0.5%.
The composition of sandwich layer are as follows: the mass percentage content of copolymer nylon 66/6T is 48.9%, MXD6-PA66 copolymer Mass percentage content is 20%, and the mass percentage content of polyphenylene sulfide is 15%, graphene in-situ polymerization modified polyphenyl sulphur The mass percentage content of ether is 10%, the quality percentage of Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer It is 6% than content, the mass percentage content of higher alcohols phosphoric acid ester sodium is 0.1%.
The composition of layer are as follows: the mass percentage content of polyphenylene sulfide is 73%, the copolymer of nylon 6 and nylon66 fiber Mass percentage content is 12%, and the mass percentage content of thermoplastic elastomer (TPE) is 8%, and glycidyl methacrylate connects The mass percentage content of branch styrenic elastomer is 5%, and the mass percentage content of higher alcohols phosphoric acid ester sodium is 0.2%, the mass percentage content of calcium carbonate is 1%, and the mass percentage content of silicone powder is 0.3%, precipitation method titanium dioxide Silicon mass percentage content is 0.5%.
Wherein, upper epidermis with a thickness of 4 μm；Sandwich layer with a thickness of 6 μm, layer is with a thickness of 5 μm.
According to the component of above layers structure, it is prepared according to aforementioned preparation process.
Comparative example 1
Commercially available 15 μm of BOPA films.
Comparative example 2
The composition of upper epidermis are as follows: the mass percentage content of polyphenylene sulfide is 70.1%, and the mass percent of nylon 612 contains Amount is 18%, and the mass percentage content of polyamide-based elastomer is 6%, and Ethylene-butyl acrylate-Glycidyl methacrylate is sweet The mass percentage content of grease copolymer is 3.5%, and the mass percentage content of Castor Oil Phosphate Ester Salt is 0.8%, carbonic acid The mass percentage content of calcium is 0.8%, and the mass percentage content of polyethylene wax is 0.4%, precipitated silica quality Degree is 0.4%.
The composition of sandwich layer are as follows: the mass percentage content of copolymer nylon 6/10 is 70.2%, the quality percentage of polyphenylene sulfide It is 10% than content, the mass percentage content of organosilicon grafted and modified polyphenylene sulfide is 15%, methyl propenoic acid glycidyl The mass percentage content of ester graft phenylethene class elastomer is 4%, and the mass percentage content of mantoquita heat stabilizer is 0.8%.
The composition of layer are as follows: the mass percentage content of polyphenylene sulfide is 81.5%, the mass percentage content of nylon 6 It is 10%, the mass percentage content of thermoplastic elastomer (TPE) is 3%, and the mass percentage content of epoxy resin is 3%, higher alcohols The mass percentage content of phosphoric acid ester sodium is 0.8%, and the mass percentage content of wollastonite is 0.8%, the matter of oleamide Measuring degree is 0.5%, and fumed silica mass percentage content is 0.4%.
Wherein, upper epidermis with a thickness of 1.5 μm；Sandwich layer with a thickness of 11 μm, layer with a thickness of 2.5 μm.
According to the component of above layers structure, it is prepared according to aforementioned preparation process.
Comparative example 3
The composition of upper epidermis are as follows: the mass percentage content of polyphenylene sulfide is 73.8%, the mass percentage content of nylon 6 It is 15%, the mass percentage content of copolymer nylon is 4%, glycidyl methacrylate graft styrenic elastomer Mass percentage content is 4.5%, and the mass percentage content of higher alcohols phosphoric acid ester sodium is 0.8%, the quality hundred of diatomite Dividing than content is 1%, and the mass percentage content of polyethylene wax is 0.4%, and precipitated silica mass percentage content is 0.5%.
The composition of sandwich layer are as follows: the mass percentage content of copolymer nylon 66/6I is the matter of 75%, MXD6-PA66 copolymer Measuring degree is 20%, and the mass percentage content of epoxy resin is 4%, the mass percent of higher alcohols phosphoric acid ester sodium Content is 1%.
The composition of layer are as follows: the mass percentage content of polyphenylene sulfide is 76.5%, nylon66 fiber mass percentage content It is 12%, the mass percentage content of thermoplastic elastomer (TPE) is 5%, Ethylene-butyl acrylate-glycidyl methacrylate The mass percentage content of copolymer is 4%, and the mass percentage content of Castor Oil Phosphate Ester Salt is 0.8%, kaolinic matter Measuring degree is 0.8%, and the mass percentage content of oleamide is 0.5%, fumed silica mass percent Content is 0.4%.
Wherein, upper epidermis with a thickness of 2 μm；Sandwich layer with a thickness of 10 μm, layer with a thickness of 3 μm.
According to the component of above layers structure, it is prepared according to aforementioned preparation process.
It should be noted that design parameter or some common agents in above-described embodiment, are the tool under present inventive concept Body embodiment or preferred embodiment, rather than its limitations；Those skilled in the art, can be in present inventive concept and protection scope It is adaptively adjusted.
Above-described embodiment and comparative example are subjected to relevant item test, test method is
Tensile property: according to GBT 1040.3-2006 standard testing；
Flame retardant property: ANSL-UL94-2009 standard testing is pressed；
Punctured resistance: GB/T10004-2008 standard testing is pressed；
Percent thermal shrinkage: GB/T12027-2004 standard testing is pressed；
Saturation water suction size changing rate: damping 48h is experiment condition in 25 DEG C, the air of 55% humidity, is tested identical The saturation water suction size changing rate of sample under size (length × width x thickness: 5cm × 5cm × 15 μm)；
OTR oxygen transmission rate: according to ASTM D3985 standard testing.
As a result as shown in the table:
Each embodiment of table 1, comparative example performance test table
Using embodiment 1-3 and comparative example 1-3 and common polyamides prepared by the present invention it can be seen from upper table result Amine film is compared, and present invention polyamide film produced has extremely low water absorption rate and has superior mechanical property, barrier Property, dimensional stability, heat resistance, fire-retardant performance.
By upper table result can also be seen that the film of comparative example 2 (MXD6-PA66 is not added in sandwich layer) improve it is fire-retardant In the case where performance, excellent mechanical property and dimensional stability are also maintained；Comparative example 3 (polyphenylene sulfide is not added in sandwich layer And modified polyphenyl thioether) film, in the case where improving the performance of blocking oxygen, also maintain excellent mechanical property and Dimensional stability.
Although more herein used the terms such as upper epidermis, sandwich layer, layer, it is not precluded using other A possibility that term.The use of these items is only for be more convenient to describe and explain essence of the invention；They are explained It at any additional limitation is disagreed with spirit of that invention.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims (10)

1. a kind of polyamide film suitable for electronic product outer packing, it is characterised in that: the polyamide film is 3 layers of knot Structure is followed successively by upper epidermis, sandwich layer, layer；
Wherein, the upper epidermis and layer include following preparing raw material: polyphenylene sulfide, nylon, toughener, compatilizer, heat Stabilizer, inorganic particulate, slipping agent, opening agent；
The sandwich layer includes following preparing raw material: copolymer nylon, MXD6-PA66 copolymer, polyphenylene sulfide, modified polyphenyl thioether, Compatilizer, heat stabilizer.
2. the polyamide film according to claim 1 suitable for electronic product outer packing, which is characterized in that the upper table Layer and layer include the raw material of following mass fraction:
The sandwich layer includes the raw material of following mass fraction:
3. the polyamide film according to claim 1 suitable for electronic product outer packing, it is characterised in that: the copolymerization Nylon is nylon 6/66, nylon66 fiber/6, nylon 6/10, nylon66 fiber/6T, nylon 6I/6T, nylon 6/6I, nylon 1010/6, nylon 10T/11, nylon 1010/66, nylon66 fiber/610, nylon 1010/66/610, nylon 6/66/610, nylon 6/611, nylon 6/ 66/12, nylon66 fiber/6I, nylon66 fiber/6T/6I is one or more.
4. the polyamide film according to claim 1 suitable for electronic product outer packing, it is characterised in that: the increasing Tough dose is thermoplastic elastomer (TPE), polyamide-based elastomer, one of copolymer nylon or a variety of.
5. the polyamide film according to claim 1 suitable for electronic product outer packing, it is characterised in that: the phase Appearance agent is glycidyl methacrylate graft styrenic elastomer, epoxy resin, Ethylene-butyl acrylate-methyl-prop One of olefin(e) acid glycidyl ester copolymer, acrylic acid-grafted polyphenylene sulfide are a variety of.
6. the polyamide film according to claim 1 suitable for electronic product outer packing, it is characterised in that: the nothing Machine particle is through Silane coupling agent KH550 treated magnesium carbonate, aluminium oxide, calcium carbonate, diatomite, talcum powder, barium sulfate, height One of ridge stone, titanium dioxide, wollastonite, silica are a variety of.
7. the polyamide film according to claim 1 suitable for electronic product outer packing, it is characterised in that: the polyphenyl Thioether is linear polyphenylene sulfide；The melt flow rate (MFR) of polyphenylene sulfide is 30~100g/ in the upper epidermis and layer 10min, fusing point are 265~290 DEG C；Polyphenylene sulfide in the sandwich layer is copolymerized polyphenylene sulfide, and fusing point is 240~265 DEG C.
8. the polyamide film according to claim 1 suitable for electronic product outer packing, it is characterised in that: the modification Polyphenylene sulfide is organosilicon grafted and modified polyphenylene sulfide, multiterminal polyhedral silsesquioxane graft modification polyphenylene sulfide, graphite One of alkene in-situ polymerization modified polyphenyl thioether is a variety of.
9. the polyamide film according to claim 1 suitable for electronic product outer packing, it is characterised in that: the upper table The dispersion particle diameter of nylon in the base is 10~400nm in layer and layer, and the inorganic particulate partial size is 0.01~4 μm；Institute The skin depth stated is 1.5~6 μm, and the polyamide film is with a thickness of 10~30 μm.
10. a kind of preparation of -9 described in any item polyamide films suitable for electronic product outer packing according to claim 1 Method, which comprises the following steps:
Step 1: each component in upper epidermis, sandwich layer and layer is mixed respectively, and it is stirred；
Step 2: by the raw material of upper epidermis, sandwich layer and layer respectively by respective extruder melting extrusion, by T-shaped mould Head outflow, and it is cooling in chilling roller, form non-stretched sheet material；
Step 3: non-stretched sheet material to be carried out to substep or synchro-draw at 60~140 DEG C, film is obtained；
Step 4: the film after stretching is carried out thermal finalization at 150~210 DEG C, and at least one surface of film is carried out Then sided corona treatment is wound, finally obtain the polyamide film.
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