CN109367044A - A kind of high-impact biaxial stretching polyester/polyamide film and preparation method thereof - Google Patents

A kind of high-impact biaxial stretching polyester/polyamide film and preparation method thereof Download PDF

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Publication number
CN109367044A
CN109367044A CN201811124333.XA CN201811124333A CN109367044A CN 109367044 A CN109367044 A CN 109367044A CN 201811124333 A CN201811124333 A CN 201811124333A CN 109367044 A CN109367044 A CN 109367044A
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polyamide
polyester
film
membrane tube
nylon
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CN109367044B (en
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Jiangyin Changgeng High-Tech Materials Co Ltd
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Jiangyin Changgeng High-Tech Materials Co Ltd
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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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/16—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial simultaneously
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/085—Layered products comprising a layer of metal comprising metal 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 comprising polyolefins
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/088—Layered products comprising a layer of metal comprising metal 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 comprising polyamides
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/09—Layered products comprising a layer of metal comprising metal 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 comprising polyesters
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment
    • B29C2071/022—Annealing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • 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
    • B32B2250/04—4 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
    • B32B2250/05—5 or more 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
    • 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
    • B32B2307/70—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
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries

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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a kind of high-impact biaxial stretching polyester/polyamide films and preparation method thereof, the described method comprises the following steps: a), multi-layer co-extruded membrane tube: the multilayered structure of membrane tube is polyester/binder/(polyamide)n；B), it is rapidly cooled to room temperature after being coextruded；C), biaxial tension: biaxial tension after membrane tube after cooling is heated up to 70-120 DEG C, draw ratio are as follows: longitudinal 2.5-4.0；Laterally: 3.0-4.0；D), be heat-treated: the membrane tube after stretching carries out annealing heat-treatment in the case where keeping vertical and horizontal tension after traction roller flattens；E), wind: by the film cooling after heat treatment, and being cut, wind to obtain finished product.High-impact biaxial stretching polyester/polyamide film of the invention is corrosion-resistant, the cold stamping shaped cladding material for haveing excellent performance, requiring suitable for new energy car battery packaging applications.

Description

A kind of high-impact biaxial stretching polyester/polyamide film and preparation method thereof
Technical field
The invention belongs to packing film technical field, be related to a kind of high-impact biaxial stretching polyester/polyamide film and its Preparation method, and a kind of aluminum-plastic composite membrane comprising it.
Background technique
Currently, lithium ion battery is common secondary cell, had been widely used in the field 3C, with electric car Development, for the housing material of lithium ion battery, more stringent requirements are proposed.Lithium ion battery outsourcing used at present Package material is composite material, structure composition are as follows: outer layer substrate layer, metal barrier, hot sealing layer composition.Wherein outer layer base material film Elongation percentage, toughness, tensile strength, the isotropic required, should overcome following problems:
1., the molding mode that is used due to lithium ion battery for cold forming, in forming process, three kinds of performance differences Material splitting easily occurs, especially between outer layer substrate layer and metal barrier, and metal barrier is in cold forming Defect is also easy to produce in journey；
2., wrapping film is when carrying out heat-sealing process, 180-200 DEG C of temperature, time 2-3s, outer layer easily occurs with this condition The splitting of substrate layer and metal barrier；
3., lithium battery used under conditions of high temperature and humidity, outer layer base material film directly contacts exceedingly odious environment, Yi Fa Raw splitting.
In addition, outer layer base material film protects metallic intermediate layer barrier layer not to be scratched, should be able to continuously grasp in process Make without disfeaturing, prevent damage of the external force to battery in use, protected in the use process of battery in Portion avoids impacting concussion caused by battery as falling etc..The outer layer base material film of lithium battery outer packing generally uses nylon Film film, but since existing nylon membrane material property itself determines its easy moisture absorption, it is not corrosion-resistant, it is difficult to meet outside lithium battery The requirement of the outer layer base material film of packaging.
Chinese patent (publication number CN107825794A) discloses the biaxial tension nylon co-extrusion film that a kind of surface layer is polyester And preparation method thereof, using the tape casting+biaxial tension technique, either synchro-draw or asynchronous stretching, longitudinal and horizontal Orientation has difference in both direction, will make polyamide film longitudinal with lateral mechanical strength disunity, and lithium ion The polyamide film needs of field of batteries application are unified in longitudinal and lateral mechanical strength, prevent in cold forming process because of vertical To the removing risk generated with lateral mechanical strength disunity.
Summary of the invention
Therefore, it is obstructed for lithium ion battery outer cover material nylon membrane in the prior art as outer layer substrate layer and metal Splitting easily occurs for layer, and the easy moisture absorption is not corrosion-resistant, it is difficult to the technical issues of meeting the requirements, the purpose of the present invention is to provide A kind of high-impact biaxial stretching polyester/polyamide film and preparation method thereof, the high-impact biaxial stretching polyester/polyamide Film is corrosion-resistant, cold stamping shaped performance and composite performance are excellent, requires suitable for new energy car battery packaging applications outer Layer material.
High-impact biaxial stretching polyester/polyamide film preparation method of the invention comprising steps of
A), multi-layer co-extruded membrane tube: by weight, by the polyester of 10%-20%, the binder and 65%- of 10%-15% Coextrusion structure is polyester/binder/(polyamide) after 80% polyamide is melted respectively by more extrudersnMulti-layer thin Wall membrane tube, membrane tube with a thickness of 100-400 μm, n=2~5；
B), it is rapidly cooled to room temperature after being coextruded, allows membrane tube to be in height amorphous state, in favor of biaxial tension；
C), biaxial tension: biaxial tension after membrane tube after cooling is heated up to 70-120 DEG C, draw ratio are as follows: longitudinal 2.5- 4.0；Laterally: 3.0-4.0；Stretch product below: stretching front product is 10:1~16:1；
D), be heat-treated: the membrane tube after stretching, in the case where keeping vertical and horizontal tension, uses after traction roller flattens Flat heater method carries out annealing heat-treatment, and heat treatment temperature is 80-230 DEG C；
E), wind: being cut after the film cooling after heat treatment, winding obtains finished product.
The method of the invention control formula is polyester 10%-20%, binder 10%-15%, polyamide 6 5%- 80%；Wherein polyester is adhered layer as centre as corrosion-resistant surface layer, binder, both raw material dosages are relatively low；And gather Amide is as structure sheaf and is more suitable for the surface layer bonded with metal barrier aluminium platinum, and dosage is relatively large, and polyamide is layered The then biaxial tension of multi-layer co-extruded membrane tube is carried out with polyester and binder, the equilibrium of macromolecule molecular chain orientation can achieve machine Tool intensity both direction balance and be easily adjusted both direction orientation ratio, the cold stamping performance that can have been kept.And And polyamide layering coextrusion when adjustment get up it is more flexible, easily facilitate realize adjustment final performance purpose.
In addition, after stretching, material can generate rebound, therefore conventional membrane tube after draw ratio is excessive when conventional production In method production process, longitudinally, laterally draw ratio is normally controlled within 3.0, and total area ratio controls within 9:1；Film needs The performance requirement that sufficiently can just meet lithium ion battery packaging material is stretched, draw ratio usually requires to reach 10:1 or more, because This conventional membrane tube production method cannot achieve.For this purpose, subsequent thermal steps are used in the present invention, to the film after stretching, It keeps heat treatment under tension to eliminate internal stress, carries out shaping, avoid material rebounds, effectively improve film performance.
In step a, multi-layer co-extruded membrane tube detailed process are as follows: Starting Material Polyester, binder, polyamide distribution are added more Extruder (is specifically assigned as polyester one, binder one, polyamide n platform), is supplied respectively to different meltings after high temperature melt Stream is converged in die head, and the thin-walled pipe of an end-closed multilayered structure is molded as by annular port, then is passed through compression Air is allowed to inflation to required thickness.
Preferably, n=3, i.e. polyamide points three layers are coextruded with polyester and binder in step a, it is coextruded the more of membrane tube Layer Structural assignments are polyester/binder/polyamide/polyamide/polyamide.
Preferably, the polyester is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), is gathered One of (ethylene naphthalate) (PEN) and polybutylene naphthalate (PBN) are also possible to two kinds or more polyester Mixing.
Preferably, the binder is improved polyalkene, vinyl-vinyl acetate copolymer (EVA), ethylene-propylene One of acid copolymer (EAA), ethylene-ethylacrylate polymer (EEA) and ethylene maleic acid anhydride copolymer (EMA) or It is two or more.
Preferably, each strata amide is independently selected from nylon 6, nylon66 fiber, nylon 11, nylon 12, nylon 610, nylon 612,12 copolymer of nylon 6,6 6- nylon, nylon MXD, aromatic polyamide, polyamidoimide, aromatic polyimide, poly- One or more of etherimide, poly maleimide and polyaminobismaleimide.
In some preferred embodiments of the invention, the polyester is polyethylene terephthalate, and the binder is Ethylene maleic acid anhydride copolymer, the polyamide are nylon 6.
Preferably, heating mode is water heating, hot gas heating or infrared heating in step c.
Preferably, in step c, biaxial orientation process are as follows: membrane tube after cooling is heated to glass transition temperature or more；Then into Row longitudinal stretching, while carrying out lateral inflation using compressed air and completing cross directional stretch.
Preferably, stretching product below in step c: stretching front product is 13:1~16:1.
Preferably, heat treatment can be carried out in two steps in step d, the membrane tube after biaxial tension is being protected after traction roller flattens In the case where holding vertical and horizontal tension, 80 DEG C of -180 DEG C of progress pre-anneal treatments are heated to, the internal stress of film is eliminated with this, Film shrunk is prevented, the pre- shrinkage phenomenon of film is eliminated；Then 100 DEG C -230 DEG C are further heated to be made annealing treatment, is made Film recrystallizes, and eliminates tissue defects, can effectively improve the mechanical performance of film.
Preferably, the membrane tube of step a preparation is with a thickness of 150-300 μm.
Preferably, the finished films that step e is obtained are with a thickness of 10-50 μm.
The object of the invention is also to provide a kind of aluminum-plastic composite membranes comprising outer layer, middle layer and internal layer, outer layer is in Adhesion is carried out by adhesive respectively between interbed, between middle layer and internal layer；It is characterized in that, outer layer is the high-impact Biaxial stretching polyester/polyamide film, middle layer are aluminium foil film, and internal layer is polypropylene film.The aluminum-plastic composite membrane have compared with Good mechanical performance, and it is not susceptible to splitting, it can be used as battery housing material.
The positive effect of the present invention is that:
The method of the invention control formula is polyester 10%-20%, binder 10%-15%, polyamide 6 5%- 80%；Wherein polyester can effectively avoid the film moisture absorption as corrosion-resistant surface layer, improve the corrosion resistance of film.And polyamide As structure sheaf and it is more suitable for the surface layer bonded with metal barrier aluminium platinum, dosage is relatively large, and polyamide is layered and gathers Ester and binder carry out the then biaxial tension of multi-layer co-extruded membrane tube, and the equilibrium of macromolecule molecular chain orientation is to reach mechanical strength Both direction balance and be easily adjusted both direction orientation ratio, the cold stamping performance that can have been kept.And polyamides Adjustment is got up more flexible when amine layering coextrusion, easily facilitates the purpose for realizing adjustment final performance.
Subsequent thermal steps are used in the present invention, to the film after stretching, heat treatment under tension are kept to eliminate internal stress, It carries out shaping, avoids material rebounds, effectively improve film performance.
To sum up, high-impact of the invention biaxial stretching polyester/polyamide film it is corrosion-resistant, it is cold stamping shaped have excellent performance, The cladding material required suitable for new energy car battery packaging applications.
Specific embodiment
In order to further illustrate the present invention, following serial specific embodiment is provided, but the present invention is not specific real by these Apply the limitation of example, any understanding person skilled in art to few modifications of the invention will can achieve it is similar as a result, this A little changes are also contained among the present invention.
Examples 1 to 7
One, film formulation
The raw material and its weight proportion of Examples 1 to 7 are as shown in table 1.Wherein polyester is preferably poly- to benzene in Examples 1 to 5 Dioctyl phthalate second diester (PET)；Binder optimal ethylene-copolymer-maleic anhydride (EMA)；The preferred nylon 6 of polyamide.Embodiment 6 It is adjusted with 7 compared to 5 raw material type of embodiment.
Two, preparation step
A), raw material multi-layer co-extruded membrane tube: is passed through into more extruders (polyester one, binder one, polyamides by formula Amine three) melt at high temperature, according to five layers of supply melting of polyester/binder/polyamide/polyamide/polyamide arrangement point Stream is converged in die head, and being molded as an end-closed structure by annular port is polyester/binder/polyamide/polyamides Amine/polyamide multilayer thin-walled pipe, then be passed through compressed air, be allowed to inflation to required thickness membrane tube, membrane tube with a thickness of 100-400μm；
B), be coextruded after be rapidly cooled to room temperature, allow membrane tube be in height randomly, amorphous state, in favor of two-way It stretches；
C), biaxial tension: biaxial tension after membrane tube after cooling is heated up to 70-120 DEG C, draw ratio are as follows: longitudinal 2.5- 4.0；Laterally: 3.0-4.0；
D), be heat-treated: the membrane tube after stretching, in the case where keeping vertical and horizontal tension, uses after traction roller flattens The mode of flat heater carries out annealing heat-treatment, and heat treatment temperature is 80-230 DEG C；
E), wind: by the film cooling after heat treatment, and being cut, wind to obtain finished product.
The composition of raw materials and technological parameter of Examples 1 to 7 are specifically as shown in table 1.
The composition of raw materials and technological parameter of 1 Examples 1 to 7 of table
Comparative example 1~5
The composition of raw materials and technological parameter of comparative example 1~4 are as shown in table 2, are comparison other with embodiment 5, and difference is:
1 raw material of comparative example uses pure polyamide, remaining is the same as embodiment 5；
2 raw material of comparative example uses pure polyester, remaining is the same as embodiment 5；
3 raw material of comparative example is same as Example 5, and in step d heat treatment, temperature is 240 degree；Remaining is the same as embodiment 5；
4 raw material of comparative example is same as Example 5, is heat-treated without step d, is directly cooled to room temperature；Remaining same embodiment 5；
Co-extrusion film, raw material, preparation step and technological parameter reference is made using curtain coating and stretch processes in comparative example 5 Embodiment 2 in patent CN107825794A.
The composition of raw materials and technological parameter of 2 comparative example 1~5 of table
The film prepared to Examples 1 to 7 and comparative example 1~5 is tested for the property, as a result as shown in Table 3 and Table 4.
The film performance parameter of 3 Examples 1 to 7 of table
The film performance parameter of 4 comparative example 1~5 of table
Note 1: cold stamping test condition: 1., sample size: 10mm*20mm；2., press machine parameter setting: pressure 0.2- 0.6MPa, speed 20-40mm/s, dwell time 2-3s.
Note 2: corrosion resistance test method: the film of Example and comparative example, surface are dripped the electrolyte of 1mL, are placed at room temperature for For 24 hours, electrolyte composition ethylene carbonate (EC): diethyl carbonate (DEC): dimethyl carbonate (DMC)=1wt%:1wt%: 1wt%, LiPF6 1mol/L (method identical with patent CN107825794A).
By table 3 and table 4 it is found that the high-impact biaxial stretching polyester-polyamide film prepared by the method for the invention not only With good elongation percentage, toughness and tensile strength, horizontal and vertical mechanical performance differs smaller and corrosion-resistant and cold punching Molded to have excellent performance, scouring depth depth is up to 3~4mm, and composite performance greatly improves, can be compound with metal barrier well, Splitting phenomenon is avoided, the cladding material required suitable for new energy car battery packaging applications.The film of this type is more It is suitable for applying in the battery of power vehicle.
And 1 raw material of comparative example, only with polyamide, rotproofness is poor.Only with polyester, cold punching is pressed into 2 raw material of comparative example Type performance is poor.Heat treatment temperature is excessively high after comparative example 3 stretches, and not thermally treated, elongation percentage, toughness after the stretching of comparative example 4 With tensile strength by larger impact, and comparative example 5 is with reference to the scheme of patent CN107825794A, by curtain coating and two-way Although co-extrusion film made of drawing process has good elongation percentage, toughness and tensile strength and corrosion resistance, longitudinal It differs greatly with lateral mechanical strength especially elongation at break, peeling easily occurs with other materials compound tense.It can by table 4 Know, the scouring depth depth of comparative example 1~5 fails to reach 3mm, and cold stamping shaped performance is not high, greatly reduces itself and metal The composite performance of barrier layer.
The preferred embodiment of the present invention has been described in detail above, but the invention be not limited to it is described Embodiment, those skilled in the art can also make various equivalent on the premise of not violating the inventive spirit of the present invention Variation or replacement, these equivalent variation or replacement are all included in the scope defined by the claims of the present application.

Claims (10)

1. a kind of preparation method of high-impact biaxial stretching polyester/polyamide film, which is characterized in that itself the following steps are included:
A), multi-layer co-extruded membrane tube: by weight, by the polyester of 10%-20%, the binder and 65%-80% of 10%-15% Polyamide melted respectively by more extruders after coextrusion structure be polyester/binder/(polyamide)nMultilayer thin-walled film Pipe, membrane tube with a thickness of 100-400 μm, n=2~5；
B), it is rapidly cooled to room temperature after being coextruded, allows coextrusion membrane tube to be in height amorphous state, in favor of two-way drawing It stretches；
C), biaxial tension: biaxial tension after membrane tube after cooling is heated up to 70-120 DEG C, draw ratio are as follows: longitudinal 2.5-4.0；It is horizontal To: 3.0-4.0；Stretch product below: stretching front product is 10:1~16:1；
D), be heat-treated: the membrane tube after stretching after traction roller flattens in the case where keeping vertical and horizontal tension, using plate Heating carries out annealing heat-treatment, and heat treatment temperature is 80-230 DEG C；
E), wind: being cut after the film cooling after heat treatment, winding obtains finished product.
2. the method as described in claim 1, which is characterized in that in step a, n=3, i.e. polyamide points three layers and polyester and glue Agent coextrusion is tied, the multilayered structure arrangement for being coextruded membrane tube is polyester/binder/polyamide/polyamide/polyamide.
3. the method as described in claim 1, which is characterized in that the polyester is polyethylene terephthalate, gathers to benzene One or more of dioctyl phthalate fourth diester, polyethylene naphthalate and polybutylene naphthalate.
4. the method as described in claim 1, which is characterized in that the binder is improved polyalkene, ethane-acetic acid ethyenyl One of ester copolymer, ethylene-acrylic acid copolymer, ethylene-ethylacrylate polymer and ethylene maleic acid anhydride copolymer Or it is two or more.
5. the method as described in claim 1, which is characterized in that each strata amide is independently selected from nylon 6, nylon66 fiber, nylon 11, nylon 12, nylon 610, nylon 612,12 copolymer of nylon 6,6 6- nylon, nylon MXD, aromatic polyamide, polyamide acyl One or both of imines, aromatic polyimide, polyetherimide, poly maleimide and polyaminobismaleimide More than.
6. the method as described in claim 1, which is characterized in that the polyester is polyethylene terephthalate, described viscous Knot agent is ethylene maleic acid anhydride copolymer, and the polyamide is nylon 6.
7. the method as described in claim 1, which is characterized in that heating mode is water heating, hot gas heating or infrared in step c Heating.
8. the method as described in claim 1, which is characterized in that in step d, stretch below product: stretch front product be 13:1~ 16:1。
9. high-impact biaxial stretching polyester/polyamide film of method preparation as described in any one of claims 1 to 8.
10. a kind of aluminum-plastic composite membrane comprising outer layer, middle layer and internal layer, between outer layer and middle layer, middle layer and internal layer it Between adhesion is carried out by adhesive respectively；It is characterized in that, outer layer be high-impact biaxial stretching polyester as claimed in claim 9/ Polyamide film, middle layer are aluminium foil film, and internal layer is polypropylene film.
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CN113334809A (en) * 2021-05-31 2021-09-03 江苏慧智新材料科技有限公司 Production process of release film base film for MLCC (multilayer ceramic capacitor) and base film
CN114905780A (en) * 2022-06-14 2022-08-16 吴云峰 Stretched base material film with small anisotropy and double-bubble production method and application thereof

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