CN106366519A - Polyvinylidene fluoride thin film and preparing method thereof - Google Patents
Polyvinylidene fluoride thin film and preparing method thereof Download PDFInfo
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- CN106366519A CN106366519A CN201610830969.0A CN201610830969A CN106366519A CN 106366519 A CN106366519 A CN 106366519A CN 201610830969 A CN201610830969 A CN 201610830969A CN 106366519 A CN106366519 A CN 106366519A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—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
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- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08K5/20—Carboxylic acid amides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/30—Fillers, e.g. particles, powders, beads, flakes, spheres, chips
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- 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
Abstract
The invention discloses a polyvinylidene fluoride thin film and a preparing method thereof. The thin film is composed of a bilayer structure of an inner layer and an outer layer which are arranged from bottom to top in sequence, wherein the inner layer adopts a flexibilizer to be subjected to toughening modification, the outer layer is a polyvinylidene fluoride layer and is made by adopting a method of multilayer salivating coextrusion or multilayer film blowing coextrusion of thermoplastic plastics. According to the polyvinylidene fluoride thin film, the inner layer is modified by the flexibilizer, which makes the thin film have better tenacity; the outer layer is polyvinylidene fluoride and does not contain PMMA or other inorganic fillers, which makes the thin film have excellent weather resistance and water vapour barrier property, so that the disadvantages of monofilm are overcome effectively.
Description
Technical field
The present invention relates to thin film materials art, more particularly, to a kind of polyvinylidene difluoride film and preparation method thereof.
Background technology
Kynoar (referred to as pvdf) is important a member in fluoroplastics family, steady due to its chemical constitution c-f key
Qualitative and higher crystallinity, polyvinylidene fluoride material has the ability of excellent opposing ultraviolet damage, and chemically-resistant is rotten
Erosion, has relatively low water vapor transmittance, is widely used in solar-energy photo-voltaic cell currently as Weatherproof ageing-resistant protecting film
In assembly backboard.Reliable backboard typically commonly uses five-layer structure, i.e. fluorine film/glue/pet/ glue/fluorine film；Fluorine film is commonly used poly- inclined
Fluorothene (pvdf) thin film or polyvinyl fluoride (pvf) thin film.The effect of fluorine film layer in backboard is: itself is weather-proof it is ensured that open air makes
Do not deteriorated with least 25 years；Meanwhile, intercept ultraviolet and intercept steam, protection inner layer material and cell piece life-time service.
With regard in the prior art of polyvinylidene difluoride film, mostly single-layer membrane structure: cn105038046a discloses one kind
Monolayer polyvinylidene difluoride film, except pvdf, with the addition of Nano filling, drip agent, polymethyl methacrylate (referred to as
The modified pvdf such as pmma)；Cn102666715a has invented a kind of good monolayer pvdf thin film of outward appearance, employs high and low melting
The formula that index pvdf compounds, improves the dispersion of inorganic filler, contains pmma, inorganic filler simultaneously；cn104059317a、
Cn104151752a has invented the white master batch of pvdf film preparation respectively.The shortcoming of single-layer membrane structure is other of interpolation
Material can substantially reduce weatherability, barrier properties for gases and the mechanical strength of pvdf, and the addition of such as pmma is so that thin film becomes
Crisp, hygroscopic, and short-term suffer from sunlight after degrade, xanthochromia etc., promote material property to deteriorate；Meanwhile, pmma fall
The degree of crystallinity of low pvdf, makes tensile strength of material decline.Due to pmma and pvdf partially compatible, and add inorganic filler, thin film
Toughness of material is very poor, is easily broken off.Cn105566818a has invented a kind of fluorine film, has two-layer structure, and side is dumb light layer, and one
Layer is tack coat, and this invention also has the shortcomings that water vapor transmittance height, film toughness are poor.
Content of the invention
One of the technical problem to be solved in the present invention is: develops a kind of polyvinylidene difluoride film, has double-decker.Internal layer
Carry out toughening modifying；The function of internal layer is to hinder ultraviolet through it is easy to bonding, has preferable toughness；Outer layer is polyvinylidene fluoride
Alkene layer；The function of outer layer is to provide excellent weatherability and effectively intercept steam.The two of the technical problem to be solved in the present invention
It is the preparation method that corresponding polyvinylidene difluoride film is provided.
Present invention aims to a kind of polyvinylidene difluoride film of above-mentioned not enough offer and preparation method thereof, make thin film
Not only there is preferable weatherability, low water vapor transmittance, film toughness is preferable simultaneously.
For achieving the above object, the technical solution used in the present invention is:
A kind of polyvinylidene difluoride film, described thin film has double-decker, described thin film from bottom to top successively by internal layer with
Outer layer coextrusion composition, described internal layer is toughening layer, carries out toughening modifying using toughener, and described outer layer is Kynoar
Layer.
Further, described double-decker thin film can be using the thermoplastic bilayer sialorrhea co-extrusion known to plastic processing industry
Go out or double-deck blown film coextrusion is realized.
Further, the toughening layer of described polyvinylidene difluoride film is to include toughener and polymethyl methacrylate
Pvdf functional layer.
Further, described toughening layer be include toughener, polymethyl methacrylate, antioxidant, white inorganic are filled out
Material and the pvdf functional layer of ultraviolet absorber.
Described outer layer is polyvinylidene fluoride layer, and preferably described polyvinylidene fluoride layer is to include the Kynoar of antioxidant
Layer.
Further, the thickness of described internal layer is 4～50 microns, and the thickness of described outer layer is 4～50 microns.
The thickness of preferably internal layer, outer layer is than for 1:0.1～10, more preferably 1:0.5～2, more preferably 1:1.
Further, described internal layer is made up of the raw material of following mass parts: 33～84.8 parts of Kynoar；Poly- methyl-prop
5～30 parts of e pioic acid methyl ester；5～20 parts of white inorganic filler；5～15 parts of toughener；0.1～1 part of antioxidant a；Ultraviolet absorber
0.1～1 part.
Described outer layer is made up of the raw material of following mass parts: 99.5～99.95 parts of Kynoar；Antioxidant b 0.05～
0.5 part.
Described Kynoar is the polyvinylidene fluoride homopolymer or common using suspension polymerization or emulsion polymerization preparation
Polymers, under 230 DEG C of temperature, load 5kg, the melt flow rate (MFR) (melt flow rate, mfr) of test is 3～30g/
10min, preferably 6～25g/10min.
Melt flow rate (MFR) (the melt flow that described polymethyl methacrylate is tested under 230 DEG C of temperature, load 5kg
Rate, mfr) it is 2～30g/10min, preferably 5～20g/10min.
Described white inorganic filler is Rutile type titanium dioxide, anatase thpe white powder, barium sulfate, lithopone, Calcium Carbonate, cunning
One of stone powder, silicon dioxide, calcium oxide, aluminium hydroxide, magnesium hydroxide, aluminium oxide or two or more mixture, preferably
For one of Rutile type titanium dioxide, anatase thpe white powder, barium sulfate, Calcium Carbonate or two or more mixing；Powder body flat
All particle diameter is 0.01 micron～5 microns, preferably 0.02～2 micron.
Described toughener is esters of acrylic acid rubber, SIS/SEBS (sebs), fluorine rubber
Glue, polyurethane elastomer (tpu), MBS terpolymer (mbs), ethyl vinyl acetate second
One of enoate copolymer (eva), chlorinated polyethylene (cpe) or two or more mixing, preferably esters of acrylic acid rubber,
One of sebs, MBS terpolymer, chlorinated polyethylene or two or more mixing
Compound.
Described antioxidant a or b each stand alone as be phenolic antioxidant, organic phosphates antioxidant, in sulphur ester antioxidant
One or more mixing, preferably 1098,168,1010,1076, dltp, one of mb, 164,264 or two kinds
Above mixture.A, b in antioxidant a or antioxidant b is used for distinguishing the antioxidant in different formulations, does not possess chemistry meaning
Justice.
Described ultraviolet absorber is salicylic acid esters, benzophenone class, benzotriazole, group-substituted acrylonitrile, triazines and is subject to
One of hindered amine or two or more mixture.It is preferably salicylic acid esters, benzotriazole, benzophenone class, triazines purple
One of outer absorbent or two or more mixture, more preferably 2- (2- hydroxy-5-methyl base phenyl)-benzotriazole, double
Salicylic acid bis-phenol a ester, 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone, 2- (2 '-methyl -4 '-hydroxy phenyl)-benzo
In triazole, the chloro- 6- of 2,4- bis- (4- morpholinyl) -1,3,5-triazines, 2- (2 '-hydroxyl -5 '-tert-butyl-phenyl)-benzotriazole
One or more mixing.
The present invention also provides the preparation method of described polyvinylidene difluoride film, and methods described is: (1) is by internal layer and outer layer
Raw material mixes through high-speed mixer, respectively obtains internal layer and outer layer compound；(2) internal layer is put into respectively with outer layer compound
Carry out melting, disperse and extruding pelletization to double screw extruder, respectively obtain internal layer and outer layer raw material particle；(3) by internal layer
After being dried with outer layer raw material particle, put in two layers of co-extrusion slobbering machine or two single-screw machine extruders of inflation film manufacturing machine respectively,
Conveyed, melted and extruded at 180～230 DEG C, and converged into rack-style casting die head or screw type film-blowing die head, die head temperature
Spend for 200～230 DEG C, through die head extrusion after-drawing, cooling and shaping, trimming winds, thus the Kynoar required for obtaining
Thin film.
Further, in preferably described step (1), mixing temperature is 30～50 DEG C, mixes rotating speed 300～1000rpm.
In preferably described step (2), the extrusion temperature of dual-screw-stem machine extruder extruding pelletization is 120～240 DEG C, and screw rod turns
Speed is 250～500rpm.
Specifically, the preparation method of polyvinylidene difluoride film preferably of the present invention follows the steps below:
(1) internal layer is mixed through high-speed mixer with outer layer raw material, mixing temperature is 30～50 DEG C, mix rotating speed 300
～1000rpm, respectively obtains internal layer and outer layer compound；(2) internal layer and outer layer compound are put into twin-screw extrusion respectively
Machine carries out melting, disperses and extruding pelletization, respectively obtains internal layer and outer layer raw material particle, and extrusion temperature is 120～240 DEG C,
Screw speed is 250～500rpm；(3), after internal layer being dried with outer layer raw material particle, two layers of co-extrusion slobbering machine are put into respectively
Or in two single-screw machine extruders of inflation film manufacturing machine, conveyed, melted and extruded at 180～230 DEG C, and converge into rack-style
Casting die head or screw type film-blowing die head, die head temperature is 200～230 DEG C, through die head extrusion after-drawing, cooling and shaping, trimming
Winding, thus the polyvinylidene difluoride film required for obtaining.
Compared with prior art beneficial effect is polyvinylidene difluoride film that the present invention provides and preparation method thereof: the present invention
Polyvinylidene difluoride film has double-decker, and internal layer is through toughening agent modified so that thin film has preferable toughness；Outer layer is poly-
Vinylidene, does not contain pmma and other inorganic fillers, makes thin film have excellent weatherability and water vapor barrier property.
Brief description
Fig. 1 is the schematic diagram of the polyvinylidene difluoride film structure of the present invention.
In figure, 1- outer layer；2- internal layer.
Specific embodiment
Referring to the drawings 1, a kind of polyvinylidene difluoride film has double-decker, includes internal layer 2 and outer layer 1 from bottom to top.Institute
Stating internal layer is toughening layer, is the pvdf functional layer comprising toughener, carries out toughening modifying using toughener, and described outer layer is poly- inclined
Fluorothene layer.During use, internal layer surface is adhesive surface, outer layer and air contact.
Kynoar is the polyvinylidene fluoride homopolymer or copolymer using suspension polymerization or emulsion polymerization preparation,
Under 230 DEG C of temperature, load 5kg, the melt flow rate (MFR) of test is 3～30g/10min.When Kynoar mfr is less than 3g/
During 10min, application viscosity is too high, is difficult to plastify, easily causes thin film became uneven；When Kynoar mfr is higher than 30g/
During 10min, because Kynoar molecular weight is too low, the mechanical property of thin film is very poor.Preferably, the mfr of Kynoar is 6
During～25g/10min, uniformly, mechanical property is qualified for thin film thickness.
The melt flow rate (MFR) that polymethyl methacrylate is tested under 230 DEG C of temperature, load 5kg is 2～30g/
10min, when polymethyl methacrylate mfr is less than 2g/10min, the system viscosity of causing is too high to be difficult melt-processed；When poly- first
When base acrylic acid methyl ester. mfr is higher than 30g/10min, thin film mechanical performance is deteriorated；Preferably, the mfr of polymethyl methacrylate
For 5～20g/10min.
Embodiment 1
The polyvinylidene difluoride film thickness that the present embodiment is provided is 8 microns, wherein: 4 microns of internal layer, 4 microns of outer layer.Interior
Layer raw material: 84.8 parts of Kynoar, 5 parts of polymethyl methacrylate, 5 parts of anatase thpe white powder, mean diameter is micro- for 0.02
Rice, 5 parts of esters of acrylic acid rubber, antioxidant 1010 is respectively 0.05 part and 0.05 part with irgasfos 168 weight portion, benzotriazole
Class ultraviolet absorber 2- (2- hydroxy-5-methyl base phenyl) 0.1 part of-benzotriazole.Outer layer raw material: 99.5 parts of Kynoar, resist
1,076 0.5 parts of oxygen agent.
The preparation method of polyvinylidene difluoride film is: internal layer is mixed through high-speed mixer by (1) with outer layer raw material, mixing
Temperature is 30 DEG C, mixes rotating speed 300rpm；(2) compound is put into double screw extruder to carry out melting, disperse to make with extrusion
Grain, obtains internal layer and outer layer raw material particle, and extrusion temperature is 120～240 DEG C, and screw speed is 250rpm.(3) by internal layer with
After outer layer raw material particle is dried, puts into respectively in two single-screw machine extruders of double-deck inflation film manufacturing machine, enter at 180～230 DEG C
Row conveying, fusing and extruding, and converge into screw type film-blowing die head, die head temperature is 200 DEG C, through die head extrusion after-drawing, cold
But shape, trimming winds, thus the polyvinylidene difluoride film a required for obtaining.
Embodiment 2
The polyvinylidene difluoride film thickness that the present embodiment is provided is 25 microns, wherein: 12.5 microns of internal layer, outer layer 12.5
Micron.Internal layer raw material: 69 parts of Kynoar, 10 parts of polymethyl methacrylate, 10 parts of Rutile type titanium dioxide, mean diameter
For 0.05 micron, 10 parts of sebs, antioxidant is 1,098 0.1 parts, and ultraviolet absorber is combining of salicylic acid esters and benzophenone class,
Salicyl salicylate (salsalate) bis-phenol a ester and 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone is divided into 0.5 part and 0.5 part；Outer layer raw material:
99.5 parts of Kynoar, 0.5 part of antioxidant dltp.
The preparation method of polyvinylidene difluoride film is: internal layer is mixed through high-speed mixer by (1) with outer layer raw material, mixing
Temperature is 40 DEG C, mixes rotating speed 650rpm；(2) compound is put into double screw extruder to carry out melting, disperse to make with extrusion
Grain, obtains internal layer and outer layer raw material particle, and extrusion temperature is 120～240 DEG C, and screw speed is 400rpm.(3) by internal layer with
After outer layer raw material particle is dried, put in two single-screw machine extruders of two layers of co-extrusion slobbering machine respectively, 180～230
DEG C conveyed, melted and extruded, and converged into rack-style casting die head die head, die head temperature is 215 DEG C, after die head extrusion
Stretching, cooling and shaping, trimming winds, thus the polyvinylidene difluoride film b required for obtaining.
Embodiment 3
The polyvinylidene difluoride film thickness that the present embodiment is provided is 50 microns, wherein: 25 microns of internal layer, outer layer 25 is micro-
Rice.Internal layer raw material: 49 parts of Kynoar, 20 parts of polymethyl methacrylate, anatase thpe white powder and barium sulfate are respectively 10
Part with 5 parts, titanium dioxide and barium sulfate mean diameter be respectively 0.05 micron with 2 microns, 15 parts of chlorinated polyethylene cpe, antioxidant
For 1,076 0.5 parts, benzotriazole ultraviolet absorber 2- (2 '-methyl -4 '-hydroxy phenyl)-benzotriazole and triazines ultraviolet
Absorbent 2, the chloro- 6- of 4- bis- (4- morpholinyl) -1,3,5-triazines is respectively 0.25 part and 0.25 part.Outer layer raw material: polyvinylidene fluoride
99.95 parts of alkene, 1,098 0.05 parts of antioxidant.
The preparation method of polyvinylidene difluoride film is: internal layer is mixed through high-speed mixer by (1) with outer layer raw material, mixing
Temperature is 50 DEG C, mixes rotating speed 1000rpm；(2) compound is put into double screw extruder to carry out melting, disperse to make with extrusion
Grain, obtains internal layer and outer layer raw material particle, and extrusion temperature is 120～240 DEG C, and screw speed is 500rpm.(3) by internal layer with
After outer layer raw material particle is dried, put in two single-screw machine extruders of two layers of co-extrusion slobbering machine respectively, 180～230
DEG C conveyed, melted and extruded, and converged into rack-style casting die head, die head temperature is 230 DEG C, extruded post-tensioning through die head
Stretch, cooling and shaping, trimming winds, thus the polyvinylidene difluoride film c required for obtaining.
Embodiment 4
The polyvinylidene difluoride film thickness that the present embodiment is provided is 100 microns, 50 microns of internal layer, 50 microns of outer layer.Interior
Layer raw material: 33 parts of Kynoar, 30 parts of polymethyl methacrylate, anatase thpe white powder is respectively 15 parts and 5 with Calcium Carbonate
Part, titanium dioxide and Calcium Carbonate mean diameter are respectively 0.02 micron and 1 micron, 10 parts and 5 respectively of esters of acrylic acid rubber and mbs
Part, antioxidant is 1,010 1 parts, and benzotriazole ultraviolet absorber 2- (2 '-hydroxyl -5 '-tert-butyl-phenyl)-benzotriazole 1
Part.Outer layer raw material: 99.95 parts of Kynoar, 1,098 0.05 parts of antioxidant.
The preparation method of polyvinylidene difluoride film is: internal layer is mixed through high-speed mixer by (1) with outer layer raw material, mixing
Temperature is 50 DEG C, mixes rotating speed 1000rpm；(2) compound is put into double screw extruder to carry out melting, disperse to make with extrusion
Grain, obtains internal layer and outer layer raw material particle, and extrusion temperature is 120～240 DEG C, and screw speed is 500rpm.(3) by internal layer with
After outer layer raw material particle is dried, put in two single-screw machine extruders of two layers of coextrusion film blowing machine respectively, 180～230
DEG C conveyed, melted and extruded, and converged into screw type film-blowing die head, die head temperature is 200 DEG C, extruded post-tensioning through die head
Stretch, cooling and shaping, trimming winds, thus the polyvinylidene difluoride film d required for obtaining.
Using the method for testing in gb/t 13022, the elongation at break of testing film.
Using the method for testing in astm f-1249, the moisture-vapor transmission of testing film.
Using the method for testing in astm e313-10, testing film experiences through ultraviolet light irradiation post yellowing index, thin film
Ultraviolet irradiation be 50kwh.
Control sample is conventional 25 microns of monolayer polyvinylidene difluoride films, and test result is summarized in table 1 below:
Table 1
Test result shows: the double-deck polyvinylidene difluoride film of present invention preparation, and the elongation at break of thin film is far longer than
Monofilm, shows that thin film has preferably toughness reinforcing；Compared with control sample, for the thin film of same thickness, polyvinylidene fluoride of the present invention
Alkene thin film has lower moisture-vapor transmission；Meanwhile, compared with control sample, polyvinylidene difluoride film of the present invention has preferably
Anti-ultraviolet ageing performance.
Claims (9)
1. a kind of polyvinylidene difluoride film it is characterised in that: described thin film has double-decker, from bottom to top successively by internal layer,
Outer layer coextrusion composition, described internal layer is toughening layer, and described toughening layer is to include toughener and polymethyl methacrylate
Pvdf functional layer；Described outer layer is the polyvinylidene fluoride layer including antioxidant.
2. polyvinylidene difluoride film according to claim 1 it is characterised in that: the thickness of described internal layer be 4～50 microns,
The thickness of described outer layer is 4～50 microns.
3. polyvinylidene difluoride film according to claim 1 it is characterised in that: described internal layer is by the raw material of following mass parts
Composition: 33～84.8 parts of Kynoar；5～30 parts of polymethyl methacrylate；5～20 parts of white inorganic filler；Toughener 5
～15 parts；0.1～1 part of antioxidant a；0.1～1 part of ultraviolet absorber.
4. polyvinylidene difluoride film according to claim 1 it is characterised in that: described outer layer is by the raw material of following mass parts
Composition: 99.5～99.95 parts of Kynoar；0.05～0.5 part of antioxidant b.
5. the polyvinylidene difluoride film according to claim 3 or 4 it is characterised in that: described Kynoar is using outstanding
The polyvinylidene fluoride homopolymer of floating polymerization or emulsion polymerization preparation or copolymer, test under 230 DEG C of temperature, load 5kg
Melt flow rate (MFR) be 3～30g/10min；Described polymethyl methacrylate is tested under 230 DEG C of temperature, load 5kg
Melt flow rate (MFR) is 2～30g/10min.
6. the polyvinylidene difluoride film according to claim 3 or 4 it is characterised in that: described antioxidant a or b is each independent
It is one of phenolic antioxidant, organic phosphates antioxidant, sulphur ester antioxidant or two or more mixing.
7. polyvinylidene difluoride film according to claim 3 it is characterised in that: described white inorganic filler be rutile-type
Titanium dioxide, anatase thpe white powder, barium sulfate, lithopone, Calcium Carbonate, Pulvis Talci, silicon dioxide, calcium oxide, aluminium hydroxide, hydrogen-oxygen
Change one of magnesium, aluminium oxide or two or more mixture.
8. polyvinylidene difluoride film according to claim 3 it is characterised in that: described ultraviolet absorber be salicylate
One of class, benzophenone class, benzotriazole, group-substituted acrylonitrile, triazines and hindered amines or two or more mixture.
9. polyvinylidene difluoride film according to claim 1 is it is characterised in that described polyvinylidene difluoride film is pressed with lower section
Method is obtained: internal layer is mixed through high-speed mixer by (1) with outer layer raw material, respectively obtains internal layer and outer layer compound；(2) will be interior
Layer and outer layer compound are put into double screw extruder respectively and are carried out melting, disperse and extruding pelletization, respectively obtain internal layer with outward
Layer raw material particle；(3) two layers of co-extrusion slobbering machine or inflation film manufacturing machine will be put into respectively after internal layer and outer layer raw material particle be dried
In two single-screw machine extruders, conveyed, melted and extruded at 180～230 DEG C, and converge into rack-style casting die head or
Screw type film-blowing die head, die head temperature is 200～230 DEG C, and through die head extrusion after-drawing, cooling and shaping, trimming winds, thus
To described polyvinylidene difluoride film.
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| CN201610830969.0A CN106366519A (en) | 2016-09-19 | 2016-09-19 | Polyvinylidene fluoride thin film and preparing method thereof |
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| CN108299772A (en) * | 2018-03-22 | 2018-07-20 | 南京君弘塑业有限公司 | A kind of polyvinylidene difluoride film and preparation method thereof |
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| CN113416330B (en) * | 2021-06-04 | 2023-05-26 | 河南联和聚邦新材料股份有限公司 | High-density high-elongation polyethylene film and preparation method thereof |
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| CN115558224A (en) * | 2021-12-29 | 2023-01-03 | 嘉兴高正新材料科技股份有限公司 | Polyvinylidene fluoride film for photovoltaic use and preparation method and application thereof |
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