CN113829714A - PA film for cold forming and manufacturing method thereof - Google Patents
PA film for cold forming and manufacturing method thereof Download PDFInfo
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- CN113829714A CN113829714A CN202111107255.4A CN202111107255A CN113829714A CN 113829714 A CN113829714 A CN 113829714A CN 202111107255 A CN202111107255 A CN 202111107255A CN 113829714 A CN113829714 A CN 113829714A
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- film
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000002344 surface layer Substances 0.000 claims abstract description 133
- 239000010410 layer Substances 0.000 claims abstract description 76
- 239000002994 raw material Substances 0.000 claims abstract description 48
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000011787 zinc oxide Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000002667 nucleating agent Substances 0.000 claims abstract description 6
- 239000004033 plastic Substances 0.000 claims description 47
- 238000003851 corona treatment Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000004806 packaging method and process Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 238000009998 heat setting Methods 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000010791 quenching Methods 0.000 claims description 13
- 230000000171 quenching effect Effects 0.000 claims description 13
- 238000005096 rolling process Methods 0.000 claims description 13
- 238000012216 screening Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 9
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- -1 polydimethylsiloxane Polymers 0.000 claims description 5
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 5
- 235000010234 sodium benzoate Nutrition 0.000 claims description 5
- 239000004299 sodium benzoate Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- CTPBWPYKMGMLGS-CIAFKFPVSA-N (3s,4s,5s,6r)-1,8-bis(4-methylphenyl)octa-1,7-diene-2,3,4,5,6,7-hexol Chemical compound C1=CC(C)=CC=C1C=C(O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=C(C)C=C1 CTPBWPYKMGMLGS-CIAFKFPVSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 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
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004080 punching Methods 0.000 abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229920006233 biaxially oriented polyamide Polymers 0.000 description 3
- 230000002457 bidirectional effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 241001455273 Tetrapoda Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- 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
-
- 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
- B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
-
- 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
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/10—Surface shaping of articles, e.g. embossing; Apparatus therefor by electric discharge treatment
-
- 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
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/08—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/121—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
- H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
- B32B2038/0028—Stretching, elongating
-
- 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
- B32B2307/70—Other properties
- B32B2307/73—Hydrophobic
-
- 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
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Thermal Sciences (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention provides a PA film for cold forming and a manufacturing method thereof, wherein the PA film is of a three-layer or five-layer structure, the three-layer structure sequentially comprises an upper surface layer, an inner layer and a lower surface layer from top to bottom, the five-layer structure sequentially comprises an upper surface layer, a first surface layer, an inner layer, a second surface layer and a lower surface layer from top to bottom, and when the PA film is of a five-layer structure, the raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: the PA film is prepared from the PA resin, the surface-modified tetrapod-like zinc oxide whiskers, the nucleating agent and the opening slipping agent, and has excellent tensile strength, elongation at break and hydrophobic property, the punching depth is more than 4mm, and the shrinkage is less than 5%.
Description
Technical Field
The invention relates to the technical field of films, in particular to a PA film for cold forming and a manufacturing method thereof.
Background
The outer packaging assembly of the soft package lithium ion battery is an aluminum-plastic composite film, and the structure of the outer packaging assembly is as follows: PA/adhesive/AL/adhesive or adhesive resin/CPP, the aluminum-plastic composite film is formed into a container through cold forming and deep drawing, the container is used for containing electrolyte, and the PA film protects the aluminum foil from generating pinholes and cracks in the cold forming and deep drawing process. The PA membrane is the substrate film of plastic-aluminum complex film, compares in general use BOPA membrane, need possess high intensity, in order to be fit for cold forming, requires the PA membrane to have fine isotropy, bears the same drawing and has the same deformation in cold forming in-process each direction like this, has fine guard action to aluminium foil AL, and the cold forming degree of depth just can be darker.
At present, domestic BOPA is produced by adopting a flat membrane method, namely a T-shaped die head and bidirectional stretching are carried out, the bidirectional stretching is carried out in the longitudinal direction and the transverse direction, the inevitable produced PA film has difference in stretching performance in the two directions, the isotropy is poor, the punching depth is not deep, and the BOPA film cannot be used for application with high punching depth requirements.
In view of this, a PA film for cold forming and a method for manufacturing the same are needed.
Disclosure of Invention
The invention aims to provide a PA film for cold forming and a manufacturing method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the PA film for cold forming is of a three-layer or five-layer structure, the three-layer structure sequentially comprises an upper surface layer, an inner layer and a lower surface layer from top to bottom, the thickness ratio of the upper surface layer to the inner layer to the lower surface layer is 1:3:1, the five-layer structure sequentially comprises an upper surface layer, a first surface layer, an inner layer to a second surface layer and a lower surface layer from top to bottom, and the thickness ratio of the upper surface layer to the first surface layer to the inner layer to the second surface layer to the lower surface layer is 2:3:10:3: 2.
Preferably, when the PA film is of a five-layer structure, the raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: 95-99% of PA resin and 1-5% of opening slipping agent, wherein the raw materials of the first surface layer, the second surface layer and the inner layer are all PA resin.
Preferably, when the PA film is of a five-layer structure, the raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: 85-90% of PA resin, 8-12% of surface modified tetrapod-like zinc oxide whisker, 1-5% of opening slipping agent and 0.1-1% of nucleating agent; the raw materials of the first secondary surface layer, the second secondary surface layer and the inner layer are all PA resin.
Preferably, the opening lubricant is selected from one or more of erucamide, stearic acid amide, oleic acid amide, talcum powder, silicon dioxide, organic siloxane and kaolin.
Preferably, the nucleating agent is selected from any one or a mixture of more of nano titanium dioxide, sodium benzoate, montmorillonite and di (p-methyl benzylidene) sorbitol.
Preferably, the preparation steps of the surface modified tetrapod-like zinc oxide whisker are as follows: dissolving polydimethylsiloxane in ethyl acetate solution, adding hydrochloric acid to adjust the pH value to acidity, carrying out water bath with constant temperature for 45-60min, carrying out reduced pressure filtration, washing, and drying to obtain the modified tetrapod-like zinc oxide whisker.
The tetrapod-like zinc oxide whisker surface contains a small amount of hydroxyl groups, can form hydrogen bonds with oxygen-containing groups in polydimethylsiloxane to form a composite material with a porous frame structure in a cross-linking manner, the porous frame structure has good mechanical stability, the tetrapod-like zinc oxide whisker contains a needle-like structure with the length of 4-10 mu m, the contact area of the composite material and water is reduced, and meanwhile, a large amount of-Si (CH) in the polydimethylsiloxane3)3，-Si(CH3)3Is a hydrophobic group, whichSo that the composite material has super-hydrophobic characteristics.
The PA film has high moisture absorption rate, poor dimensional stability and thermal stability, and the tensile strength and the shrinkage performance of the film are reduced after water absorption, so the invention introduces the surface-modified tetrapod-shaped zinc oxide whisker with super-hydrophobic property and high stability as the PA film filler, improves the film performance, reduces the surface energy of the modified tetrapod-shaped zinc oxide whisker, enhances the compatibility with PA granules, and simultaneously has a unique three-dimensional tetrapod structure to ensure that the tetrapod-shaped zinc oxide whisker has good isotropy, thus the film bears the same stretching in all directions in the cold forming process, has the same deformation and has deeper cold forming depth.
A manufacturing method of a PA film for cold forming comprises the following steps:
s1: vacuum sucking and mixing raw materials of each layer of the film, respectively melting the raw materials into a plastic body in a plurality of extruders, screening the plastic body by a filter screen and a perforated plate, co-extruding the plastic body into a multi-layer tubular film blank by a circular die head, and carrying out quenching cooling by using cold water at the temperature of 0-10 ℃;
s2, preheating the film tube blank in a temperature range of 75-120 ℃, introducing compressed air for transverse inflation, and simultaneously stretching longitudinally by drawing, wherein the transverse and longitudinal stretching ratio is controlled to be 2.8-4.0.
S3: and flattening the blown and stretched film tube blank by a traction roller, performing heat setting treatment at the temperature of 230 ℃ under the condition of keeping the longitudinal and transverse clamping relaxation state, and performing corona treatment on the surface layer of the film.
S4: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
Preferably, the method for manufacturing the PA film for cold forming includes the steps of:
s1: absorbing and mixing raw materials of each layer of the film under a vacuum condition, respectively melting the raw materials in an extruder to form a plastic body, screening the plastic body by a filter screen and a perforated plate, then co-extruding the plastic body into a multilayer tubular film blank by a circular die head, applying ultrasonic waves vertical to the plastic body at the die head, and carrying out quenching cooling by using cold water at the temperature of 0-10 ℃;
applying ultrasonic vibration perpendicular to the melt at the die head is beneficial to enhancing the isotropy in the flow direction of the melt.
S2: preheating a film tube blank within the temperature range of 75-120 ℃, introducing compressed air for transverse inflation, and simultaneously longitudinally stretching by traction, wherein the transverse and longitudinal stretching ratio is controlled to be 2.8-4.0;
s3: measuring the thickness of different positions of the film tube blank by using an online non-contact thickness gauge, determining the position with uneven film thickness, performing micro two-dimensional stretching on the position with uneven film thickness, applying ultrasonic waves in the vertical direction to the film tube blank, and performing ultrasonic vibration for 25-35 min;
the ultrasonic vibration is used for eliminating the internal stress of the film tube blank.
S4: and flattening the film tube blank subjected to the ultrasonic vibration by a traction roller, performing heat setting treatment at the temperature of 230 ℃ under the condition that the longitudinal and transverse edges are clamped and in a loose state, and performing corona treatment on the surface layer of the film.
S5: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
Preferably, the film has a thickness of 10-50 um.
The invention has the beneficial effects that:
1. the method adopts polydimethylsiloxane to modify the tetrapod-like zinc oxide whiskers to form a porous framework structure, the structure has good structural stability, and a large number of hydrophobic groups are introduced, and the prepared surface-modified tetrapod-like zinc oxide whiskers have super-hydrophobicity because the tetrapod-like zinc oxide whiskers contain a large number of needle structures and have small contact surface with water.
2. The PA film is prepared from the PA resin, the surface-modified tetrapod-like zinc oxide whiskers, the nucleating agent and the opening slipping agent, and has excellent tensile strength, elongation at break and hydrophobic property, the drawing depth is more than 4mm, and the shrinkage is less than 5%.
Detailed description of the preferred embodiments
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
For ease of understanding, the following examples are given by way of illustration only:
example 1
The invention provides a PA film for cold forming, which sequentially comprises an upper surface layer, an inner layer and a lower surface layer from top to bottom, wherein the thicknesses of the upper surface layer, the inner layer and the lower surface layer are 3um, 9um and 3um, and the thickness of the PA film is 15 um.
The raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: 95% of PA resin, 5% of erucamide and the inner layer is made of PA resin.
A manufacturing method of a PA film for cold forming comprises the following steps:
s1: vacuum sucking and mixing raw materials of each layer of the film, respectively melting the raw materials into a plastic body in a plurality of extruders, screening the plastic body by a filter screen and a perforated plate, co-extruding the plastic body into a multi-layer tubular film blank by a circular die head, and carrying out quenching cooling by using cold water at 0 ℃;
and S2, preheating the film tube blank in a temperature range of 75 ℃, introducing compressed air for transverse inflation, and simultaneously longitudinally stretching by drawing, wherein the transverse and longitudinal stretching ratio is controlled to be 2.8.
S3: and flattening the blown and stretched film tube blank by a drawing roller, performing heat setting treatment at 180 ℃ in a loose state of clamping the two longitudinal and transverse sides, and performing corona treatment on the surface layer of the film.
S4: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
Example 2
The invention provides a PA film for cold forming, which sequentially comprises an upper surface layer, an inner layer and a lower surface layer from top to bottom, wherein the thicknesses of the upper surface layer, the inner layer and the lower surface layer are 5um, 15um and 5um, and the thickness of the PA film is 25 um.
The raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: 98% of PA resin, 2% of erucamide and the raw material of the inner layer is PA resin.
A manufacturing method of a PA film for cold forming comprises the following steps:
s1: vacuum sucking and mixing raw materials of each layer of the film, respectively melting the raw materials into a plastic body in a plurality of extruders, screening the plastic body by a filter screen and a perforated plate, then co-extruding the plastic body into a multi-layer tubular film blank by a circular die head, and carrying out quenching cooling by cold water at 5 ℃;
and S2, preheating the film tube blank in a temperature range of 90 ℃, introducing compressed air for transverse inflation, and simultaneously longitudinally stretching by traction, wherein the transverse and longitudinal stretching ratio is controlled to be 3.0.
S3: and flattening the blown and stretched film tube blank by a drawing roller, performing heat setting treatment at 200 ℃ in a loose state of clamping the longitudinal and transverse sides, and performing corona treatment on the surface layer of the film.
S4: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
Example 3
The invention provides a PA film for cold forming, which sequentially comprises an upper surface layer, a first surface layer, an inner layer, a second surface layer and a lower surface layer from top to bottom, wherein the thicknesses of the upper surface layer, the first surface layer, the inner layer, the second surface layer and the lower surface layer are 3um, 4.5um, 15um, 4.5um and 3um, and the thickness of the PA film is 30 um.
The raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: 99% of PA resin and 1% of erucamide, and the raw materials of the first surface layer, the inner layer and the second surface layer are all PA resin.
A manufacturing method of a PA film for cold forming comprises the following steps:
s1: vacuum sucking and mixing raw materials of each layer of the film, respectively melting the raw materials into a plastic body in a plurality of extruders, screening the plastic body by a filter screen and a perforated plate, then co-extruding the plastic body into a multi-layer tubular film blank by a circular die head, and carrying out quenching cooling by using cold water at 8 ℃;
and S2, preheating the film blank tube in a temperature range of 120 ℃, introducing compressed air for transverse inflation, and simultaneously longitudinally stretching by traction, wherein the transverse and longitudinal stretching ratio is controlled to be 4.0.
S3: and flattening the blown and stretched film tube blank by a drawing roller, performing heat setting treatment at 230 ℃ in a loose state of clamping the two longitudinal and transverse sides, and performing corona treatment on the surface layer of the film.
S4: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
Example 4
The invention provides a PA film for cold forming, which sequentially comprises an upper surface layer, a first surface layer, an inner layer, a second surface layer and a lower surface layer from top to bottom, wherein the thicknesses of the upper surface layer, the first surface layer, the inner layer, the second surface layer and the lower surface layer are 2.5um, 3.75um, 12.5um, 3.75um and 2.5um, and the thickness of the PA film is 25 um.
The raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: 98% of PA resin, 2% of erucamide, and the raw materials of the first surface layer, the second surface layer and the inner layer are all PA resin.
A manufacturing method of a PA film for cold forming comprises the following steps:
s1: vacuum sucking and mixing raw materials of each layer of the film, respectively melting the raw materials into a plastic body in a plurality of extruders, screening the plastic body by a filter screen and a perforated plate, then co-extruding the plastic body into a multi-layer tubular film blank by a circular die head, and carrying out quenching cooling by using cold water at 10 ℃;
and S2, preheating the film tube blank in a temperature range of 100 ℃, introducing compressed air for transverse inflation, and simultaneously longitudinally stretching by drawing, wherein the transverse and longitudinal stretching ratio is controlled to be 3.5.
S3: and flattening the blown and stretched film tube blank by a drawing roller, performing heat setting treatment at 210 ℃ in a loose state of clamping the longitudinal and transverse sides, and performing corona treatment on the surface layer of the film.
S4: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
Example 5
The invention provides a PA film for cold forming, which sequentially comprises an upper surface layer, a first surface layer, an inner layer, a second surface layer and a lower surface layer from top to bottom, wherein the thicknesses of the upper surface layer, the first surface layer, the inner layer, the second surface layer and the lower surface layer are 2.5um, 3.75um, 12.5um, 3.75um and 2.5um, and the thickness of the PA film is 25 um.
The raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: 85% of PA resin, 12% of surface modified tetrapod-like zinc oxide whisker, 2% of erucamide and 1% of sodium benzoate, and the raw materials of the first surface layer, the second surface layer and the inner layer are all PA resin.
A manufacturing method of a PA film for cold forming comprises the following steps:
s1: absorbing and mixing raw materials of each layer of the film under a vacuum condition, respectively melting the raw materials into a plastic body in a plurality of extruders, screening the plastic body by a filter screen and a perforated plate, then co-extruding the plastic body into a multi-layer tubular film blank by a circular die head, applying ultrasonic waves vertical to the plastic body at the die head, and carrying out quenching cooling by using cold water at the temperature of 0 ℃;
s2: preheating a film tube blank within a temperature range of 75 ℃, introducing compressed air for transverse inflation, and simultaneously longitudinally stretching by traction, wherein the transverse and longitudinal stretching ratio is controlled to be 2.8;
s3: measuring the thickness of the film tube blank at different positions by using an online thickness gauge, determining the position with uneven film thickness, performing micro two-dimensional stretching on the position with uneven film thickness, applying ultrasonic waves in the vertical direction to the film tube blank, and performing ultrasonic vibration for 25 min;
s4: and flattening the film tube blank subjected to ultrasonic vibration by a traction roller, performing heat setting treatment at 180 ℃ in a loose state of clamping the two longitudinal and transverse sides, and performing corona treatment on the surface layer of the film.
S5: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
Example 6
The invention provides a PA film for cold forming, which sequentially comprises an upper surface layer, a first surface layer, an inner layer, a second surface layer and a lower surface layer from top to bottom, wherein the thicknesses of the upper surface layer, the first surface layer, the inner layer, the second surface layer and the lower surface layer are 1um, 1.5um, 5um, 1.5um and 1um, and the thickness of the PA film is 10 um.
The raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: 88% of PA resin, 10% of surface modified tetrapod-like zinc oxide whisker, 1% of erucamide and 1% of sodium benzoate, and the raw materials of the first surface layer, the second surface layer and the inner layer are all PA resin.
A manufacturing method of a PA film for cold forming comprises the following steps:
s1: absorbing and mixing raw materials of each layer of the film under a vacuum condition, respectively melting the raw materials into a plastic body in a plurality of extruders, screening the plastic body by a filter screen and a perforated plate, then co-extruding the plastic body into a multi-layer tubular film blank by a circular die head, applying ultrasonic waves vertical to the plastic body at the die head, and carrying out quenching cooling by using cold water at the temperature of 0 ℃;
s2: preheating a film tube blank within a temperature range of 75 ℃, introducing compressed air for transverse inflation, and simultaneously longitudinally stretching by traction, wherein the transverse and longitudinal stretching ratio is controlled to be 3.2;
s3: measuring the thickness of the film tube blank at different positions by using an online thickness gauge, determining the position with uneven film thickness, performing micro two-dimensional stretching on the position with uneven film thickness, applying ultrasonic waves in the vertical direction to the film tube blank, and performing ultrasonic vibration for 30 min;
s4: and flattening the film tube blank subjected to ultrasonic vibration by a traction roller, performing heat setting treatment at 200 ℃ in a loose state of clamping the longitudinal and transverse sides, and performing corona treatment on the surface layer of the film.
S5: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
Example 7
The invention provides a PA film for cold forming, which sequentially comprises an upper surface layer, a first surface layer, an inner layer, a second surface layer and a lower surface layer from top to bottom, wherein the thicknesses of the upper surface layer, the first surface layer, the inner layer, the second surface layer and the lower surface layer are 5um, 7.5um, 25um, 7.5um and 5um, and the thickness of the PA film is 50 um.
The raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: 90% of PA resin, 8% of surface modified tetrapod-like zinc oxide whisker, 1.9% of erucamide and 0.1% of sodium benzoate, wherein the raw materials of the first surface layer, the second surface layer and the inner layer are all PA resin.
A manufacturing method of a PA film for cold forming comprises the following steps:
s1: absorbing and mixing raw materials of each layer of the film under a vacuum condition, respectively melting the raw materials into a plastic body in a plurality of extruders, screening the plastic body by a filter screen and a perforated plate, then co-extruding the plastic body into a multi-layer tubular film blank by a circular die head, applying ultrasonic waves vertical to the plastic body at the die head, and carrying out quenching cooling by using cold water at 10 ℃;
s2: preheating a film blank within a temperature range of 120 ℃, introducing compressed air for transverse inflation, and simultaneously longitudinally stretching by traction, wherein the transverse and longitudinal stretching ratio is controlled at 4.0;
s3: measuring the thickness of different positions of the membrane tube by using an online thickness gauge, determining the position with uneven membrane thickness, performing micro two-dimensional stretching on the position with uneven membrane thickness, applying ultrasonic waves in the vertical direction to the membrane tube, and performing ultrasonic vibration for 35 min;
s4: and flattening the ultrasonically-vibrated film tube by a drawing roller, performing heat setting treatment at 230 ℃ in a loose state of clamping the two longitudinal and transverse sides, and performing corona treatment on the surface layer of the film.
S5: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
Comparative example 1
The present comparative example differs from example 4 in that the PA film of the present comparative example is manufactured as follows.
A manufacturing method of a PA film for cold forming comprises the following steps:
s1: vacuum sucking and mixing raw materials of each layer of the film, respectively melting the raw materials into a plastic body in a plurality of extruders, screening the plastic body by a filter screen and a perforated plate, co-extruding the plastic body into a multi-layer tubular film blank by a circular die head, and carrying out quenching cooling by using cold water at 10 ℃;
s2: longitudinal stretching at 60 ℃ with a stretching ratio of 3.5, and then transverse stretching at 100 ℃ with a stretching ratio of 3.5;
s3: after being flattened by a traction roller, the film blank is subjected to heat setting treatment at 210 ℃ in a loose state of being clamped at the longitudinal side and the transverse side, and the surface layer of the film is subjected to corona treatment.
S4: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
Comparative example 2
This comparative example differs from example 4 in that the PA film was manufactured as follows.
S1: vacuum sucking and mixing raw materials of each layer of the film, respectively melting the raw materials into a plastic body in a plurality of extruders, screening the plastic body by a filter screen and a perforated plate, co-extruding the plastic body into a multi-layer tubular film blank by a circular die head, and carrying out quenching cooling by using cold water at 10 ℃;
s2: preheating a film tube blank at 100 ℃, and then performing bidirectional synchronous stretching;
s3: after being flattened by a traction roller, the film blank is subjected to heat setting treatment at 210 ℃ in a loose state of being clamped at the longitudinal side and the transverse side, and the surface layer of the film is subjected to corona treatment.
S4: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
Comparative example 3
This comparative example differs from example 5 in that no surface-modified tetrapod zinc oxide whiskers were added to the PA film.
The PA films obtained in the examples and comparative examples were subjected to a thickness test in accordance with ASTM F2251; tensile strength testing was performed according to ASTM D882; carrying out shrinkage rate test on the film by water bath for 30min at 100 ℃; the punching depth test is carried out by adopting a punching machine, the pressure of the punching machine is 30MPa, the speed is 30mm/s, the pressure maintaining time is 2s, and the test results are as follows:
TABLE 1
TABLE 2
As can be seen from tables 1 and 2, the PA film for cold forming prepared by the method of the invention has good tensile strength, elongation at break, shrinkage and hydrophobic property, and the cold forming drawing depth is more than 5mm, when the PA film is used for preparing an aluminum-plastic composite film, the PA film can effectively protect an aluminum foil from generating pinholes and cracks, and has excellent isotropy, so that the PA film can bear the same stretching and deformation in all directions during the cold forming process, and has good protection effect on the aluminum foil.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (9)
1. A PA film for cold forming is characterized in that: the PA film is of a three-layer or five-layer structure, the three-layer structure sequentially comprises an upper surface layer, an inner layer and a lower surface layer from top to bottom, the thickness ratio of the upper surface layer to the inner layer to the lower surface layer is 1:3:1, the five-layer structure sequentially comprises an upper surface layer, a first surface layer, an inner layer, a second surface layer and a lower surface layer from top to bottom, and the thickness ratio of the upper surface layer to the first surface layer to the inner layer to the second surface layer to the lower surface layer is 2:3:10:3: 2.
2. The PA film for cold forming according to claim 1, wherein: when the PA film is of a five-layer structure, the raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: 95-99% of PA resin and 1-5% of opening slipping agent, wherein the raw materials of the first surface layer, the second surface layer and the inner layer are all PA resin.
3. The PA film for cold forming according to claim 1, wherein: when the PA film is of a five-layer structure, the raw materials of the upper surface layer and the lower surface layer comprise the following components in percentage by mass: 85-90% of PA resin, 8-12% of surface modified tetrapod-like zinc oxide whisker, 1-5% of opening slipping agent and 0.1-1% of nucleating agent; the raw materials of the first secondary surface layer, the second secondary surface layer and the inner layer are all PA resin.
4. The PA film for cold forming according to claim 2, wherein: the opening slipping agent is selected from one or more of erucamide, stearic acid amide, oleic acid amide, talcum powder, silicon dioxide, organic siloxane and kaolin.
5. The PA film for cold forming according to claim 3, wherein: the nucleating agent is selected from any one or a mixture of more of nano titanium dioxide, sodium benzoate, montmorillonite and di (p-methyl benzylidene) sorbitol.
6. The PA film for cold forming according to claim 3, wherein: the preparation steps of the surface modified tetrapod-like zinc oxide whisker are as follows: dissolving polydimethylsiloxane in ethyl acetate solution, adding hydrochloric acid to adjust the pH value to acidity, carrying out water bath with constant temperature for 45-60min, carrying out reduced pressure filtration, washing, and drying to obtain the modified tetrapod-like zinc oxide whisker.
7. A method for manufacturing a PA film for cold forming according to any one of claims 1 to 6, comprising the steps of:
s1: vacuum sucking and mixing raw materials of each layer of the film, respectively melting the raw materials into a plastic body in a plurality of extruders, screening the plastic body by a filter screen and a perforated plate, co-extruding the plastic body into a multi-layer tubular film blank by a circular die head, and carrying out quenching cooling by using cold water at the temperature of 0-10 ℃;
s2, preheating the film tube blank in a temperature range of 75-120 ℃, introducing compressed air for transverse inflation, and simultaneously stretching longitudinally by drawing, wherein the transverse and longitudinal stretching ratio is controlled to be 2.8-4.0.
S3: and flattening the blown and stretched film tube blank by a traction roller, performing heat setting treatment at the temperature of 230 ℃ under the condition of keeping the longitudinal and transverse clamping relaxation state, and performing corona treatment on the surface layer of the film.
S4: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
8. The method for manufacturing a PA film for cold forming according to claim 7, comprising the steps of:
s1: absorbing and mixing raw materials of each layer of the film under a vacuum condition, respectively melting the raw materials in an extruder to form a plastic body, screening the plastic body by a filter screen and a perforated plate, then co-extruding the plastic body into a multilayer tubular film blank by a circular die head, applying ultrasonic waves vertical to the plastic body at the die head, and carrying out quenching cooling by using cold water at the temperature of 0-10 ℃;
s2: preheating a film tube blank within the temperature range of 75-120 ℃, introducing compressed air for transverse inflation, and simultaneously longitudinally stretching by traction, wherein the transverse and longitudinal stretching ratio is controlled to be 2.8-4.0;
s3: measuring the thickness of the film tube blank at different positions by using an online thickness gauge, determining the position with uneven film thickness, performing micro two-dimensional stretching on the position with uneven film thickness, applying ultrasonic waves in the vertical direction to the film tube blank, and performing ultrasonic vibration for 25-35 min;
s4: and flattening the film tube blank subjected to the ultrasonic vibration by a traction roller, performing heat setting treatment at the temperature of 230 ℃ under the condition that the longitudinal and transverse edges are clamped and in a loose state, and performing corona treatment on the surface layer of the film.
S5: and rolling the film subjected to corona treatment, slitting and packaging to obtain a finished product.
9. The PA film for cold forming according to claim 8, wherein: the thickness of the PA film is 10-50 um.
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Cited By (1)
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