CN106541656A - It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film and preparation method thereof - Google Patents
It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film and preparation method thereof Download PDFInfo
- Publication number
- CN106541656A CN106541656A CN201610830875.3A CN201610830875A CN106541656A CN 106541656 A CN106541656 A CN 106541656A CN 201610830875 A CN201610830875 A CN 201610830875A CN 106541656 A CN106541656 A CN 106541656A
- Authority
- CN
- China
- Prior art keywords
- layer
- extruded
- parts
- outer layer
- middle level
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- B32B27/30—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses it is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film and preparation method thereof, thin film is made up of internal layer, middle level, outer layer three-decker from bottom to top successively, the internal layer is tack coat, the middle level is UV-blocking layer, the outer layer is PVDF layers, is coextruded using three laminar flow saliva of thermoplastic or three layers of blown film are coextruded method and prepare.The present invention it is three-layer co-extruded go out polyvinylidene difluoride film in, internal layer is the blend of PVDF and PMMA, and PMMA substantially improves the adhesive property of PVDF, therefore internal layer membrane has good adhesive property, is conducive to the surface strong bond of thin film and guard block；Middle level absorbs ultraviolet by adding ultraviolet absorber；And also white inorganic filler can be added, effectively hinder ultraviolet to pass through.Outer layer is PVDF layers, based on PVDF, does not contain PMMA, with excellent weatherability and water vapor barrier property.
Description
Technical field
The present invention relates to thin film materials art, more particularly to a kind of multi-layer co-extruded plastics thin film, specifically refer to a kind of three layers
It is coextruded 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 have the ability of excellent opposing ultraviolet damage, and chemically-resistant is rotten
Erosion, with relatively low water vapor transmittance, currently as Weatherproof ageing-resistant protecting film in photovoltaic industry, building trade, change
Extensively apply in work field etc..PVDF thin film is usually placed in the outer surface of required guard block in use, straight with air
Contact, and receive the irradiation of sunlight.Meanwhile, the combination of PVDF thin film and part is generally bonded by glue, i.e., in thin film
Surface coats one layer of glue in advance, then with protected adhering components.Therefore, for the performance requirement of PVDF thin film is：It is interior
Surface has good adhesive property, and at the same time thin film should have good weatherability with to anti-ultraviolet destruction.
In with regard to 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
) etc. PMMA increased the toughness of thin film；CN102666715A has invented a kind of good monolayer PVDF thin film of outward appearance, employs
The formula of high and low melt index PVDF compounding, improves the dispersion of inorganic filler；CN104059317A, CN104151752A distinguish
The white master batch of PVDF thin film preparation is invented.The shortcoming of single-layer membrane structure is that other materials of addition can substantially reduce material
The weatherability of material, barrier properties for gases and mechanical strength, the addition of such as PMMA so that thin film is hygroscopic, and short-term are subjected to too
There is degraded, xanthochromia etc. after sunlight irradiation, promote material property to deteriorate.
The content of the invention
One of the technical problem to be solved in the present invention is：Develop it is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film, it is interior
Layer is tack coat, with good adhesion；Middle level is ultraviolet-resistant layer, hinders ultraviolet to pass through；Outer layer be PVDF layers, it is weather-proof and
Intercept steam.Three-layer composite structure can overcome the shortcoming of single-layer membrane structure.The two of the technical problem to be solved in the present invention are to carry
For it is corresponding it is three-layer co-extruded go out polyvinylidene difluoride film preparation method.
It is an object of the invention to provide it is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film, be provided simultaneously with thin film good
Caking property and weatherability, overcome the shortcoming of single thin film.
For achieving the above object, the technical solution used in the present invention is：
It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film, the thin film is from bottom to top successively by internal layer, middle level, three layers of outer layer
Structure is coextruded composition, and the internal layer is tack coat, and the middle level is UV-blocking layer, and the outer layer is PVDF layers.
It is described it is three-layer co-extruded go out polyvinylidene difluoride film by be coextruded be obtained, further, the present invention Kynoar
Thin film is prepared by the way of the coextrusion of three laminar flow saliva of thermoplastic known to plastic processing industry or three layers of blown film are coextruded.
Further, the tack coat is the PVDF functional layers for including polymethyl methacrylate；
Further, the UV-blocking layer is the PVDF functional layers for including ultraviolet absorber；More preferably include
The PVDF functional layers of ultraviolet absorber and antioxidant；More preferably ultraviolet-resistant layer is to include polymethyl methacrylate, white
In inorganic filler one or two, the PVDF functional layers of ultraviolet absorber and antioxidant；
Further, the outer layer PVDF layers are preferably the PVDF layers for including antioxidant；Outer layer PVDF layers can also contain
White inorganic filler.
Further, the thickness of the internal layer is 2～20 microns, and the thickness in the middle level is 6～60 microns, the outer layer
Thickness is 2～20 microns.
It is preferred that internal layer, middle level, outer layer thickness ratio be 1:0.5～5:0.5～2, preferably 1:1～5:0.5～1.5, more
Preferably 1:1～5：1, more preferably 1:3:1.
Further, the internal layer includes the raw material of following mass parts：40～90 parts of Kynoar；Polymethylacrylic acid
10～60 parts of methyl ester, the composition of raw materials of preferred internal layer are made up of the raw material of following mass parts：40～90 parts of Kynoar；Poly- first
10～60 parts of base acrylic acid methyl ester., more preferably 65～90 parts of Kynoar；10～35 parts of polymethyl methacrylate.
The middle level includes the raw material of following mass parts：49.9～96 parts of Kynoar；Antioxidant A0.05～1 part；It is purple
0.05～3 part of outer absorbent.
The middle level raw material can also be including one or two in polymethyl methacrylate, white inorganic filler A
Mixing；
Further, the formula of the raw material in the middle level is preferably：
Middle layer formula ()：49.9～96 parts of Kynoar；Antioxidant A0.05～1 part；Ultraviolet absorber 0.05～3
Part；
Middle layer formula (two)：49.9～96 parts of Kynoar；Antioxidant A0.05～1 part；Ultraviolet absorber 0.05～3
Part；0.1～20 part of polymethyl methacrylate；
Middle layer formula (three)：49.9～96 parts of Kynoar；0.05～1 part of antioxidant A；Ultraviolet absorber 0.05～3
Part；0.1～30 part of white inorganic filler A
49.9～96 parts of middle layer formula (four) Kynoar；0.05～1 part of antioxidant A；Ultraviolet absorber 0.05～3
Part；0.1～20 part of polymethyl methacrylate；0.1～30 part of white inorganic filler A.
Further, the formula of the preferably raw material in the middle level is：49.9～96 parts of Kynoar；Antioxidant A 0.05
～1 part；0.05～3 part of ultraviolet absorber；0.1～20 part of polymethyl methacrylate；0.1～30 part of white inorganic filler A,
More preferably 60～90 parts of Kynoar；0.05～1 part of antioxidant A；1～3 part of ultraviolet absorber；Poly-methyl methacrylate
5～20 parts of ester；5～30 parts of white inorganic filler A；More preferably 63～73 parts of Kynoar；0.05～1 part of antioxidant A；
1.5～3 parts of ultraviolet absorber；10～20 parts of polymethyl methacrylate；15～30 parts of white inorganic filler A.
The outer layer includes the raw material of following mass parts：89～99.95 parts of Kynoar；0.05～1 part of antioxidant B.
The outer layer raw material can also include white inorganic filler B.
The formula of the outer layer is preferably：
89～99.95 parts of outer layer formula () Kynoar；0.05～1 part of antioxidant B；
89～99.95 parts of outer layer formula (two) Kynoar；0.1～10 part of white inorganic filler B；Antioxidant B
0.05～1 part.
The Kynoar is the polyvinylidene fluoride homopolymer or common prepared using suspension polymerization or emulsion polymerization
Polymers, the melt flow rate (MFR) tested under 230 DEG C of temperature, load 5kg (Melt Flow Rate, MFR) are 2～30g/
10min, preferably 6～25g/10min.
Melt flow rate (MFR) (the Melt Flow that the polymethyl methacrylate is tested under 230 DEG C of temperature, load 5kg
Rate, MFR) for 2～30g/10min, preferably 5～20g/10min.
The antioxidant A or antioxidant B each stand alone as phenolic antioxidant, organic phosphates antioxidant, sulphur ester antioxidant
In one or more mixing, preferably 1098,168,1010,1076, DLTP, the one kind or two in MB, 164,264
Plant the mixture of the above.A, B in antioxidant A or antioxidant B is used to distinguish the antioxidant in different formulations, does not possess chemical meaning
Justice.
The white inorganic filler A or white inorganic filler B each stand alone as Rutile type titanium dioxide, anatase titanium dioxide
In powder, barium sulfate, lithopone, Calcium Carbonate, Pulvis Talci, silicon dioxide, calcium oxide, aluminium hydroxide, magnesium hydroxide, aluminium oxide one
Plant or two or more mixture, preferably the one kind in Rutile type titanium dioxide, anatase thpe white powder, barium sulfate, Calcium Carbonate
Or two or more mixing；The mean diameter of powder body is 0.01 micron～5 microns, preferably 0.02～2 micron.
A, B in white inorganic filler A or white inorganic filler B is used to distinguish the white inorganic filler in different formulations,
Do not possess chemical sense.
The ultraviolet absorber is salicylic acid esters, benzophenone class, benzotriazole, group-substituted acrylonitrile, triazines and receives
One or more mixture in hindered amine ultraviolet absorber, preferably salicylic acid esters, benzophenone class, benzotriazole
One or more mixture in class, triazines ultraviolet absorber, more preferably 2- (2- hydroxy-5-methyl base phenyl)-
Benzotriazole, 2- (2 '-methyl -4 '-hydroxy phenyl)-benzotriazole, 2- (2 '-hydroxyl -5 '-tert-butyl-phenyl)-benzotriazole,
Double acid double phenol A ester, 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone, 2,4-, bis- chloro- 6- (4- morpholinyls) -1,3,
One or more mixing in 5- triazines.
The present invention also provide it is described it is three-layer co-extruded go out polyvinylidene difluoride film preparation method, methods described is：(1) will
Internal layer, middle level are mixed respectively through high-speed mixer with outer layer raw material, respectively obtain internal layer, middle level, outer layer compound；(2) will
Internal layer, middle level, outer layer compound are put into double screw extruder respectively and carry out melting, disperse and extruding pelletization, respectively obtain interior
Layer, middle level and outer layer raw material particle；(3), after by the drying of internal layer, middle level and outer layer raw material particle, put into respectively three-layer co-extruded
In three single-screw machine extruders of slobbering machine or inflation film manufacturing machine, 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 are 210～230 DEG C, and the extrusion after-drawing of Jing die heads, cooling are fixed
Type, trimming winding, so as to obtain described three-layer co-extruded polyvinylidene difluoride film；
Further, preferably in the step (1), mixing temperature is 15～60 DEG C, mixes 300～1000rpm of rotating speed.
It is preferred that in the step (2), the extrusion temperature of double screw extruder extruding pelletization is 120～240 DEG C, screw speed
For 200～500rpm.
Specifically, preferably it is of the present invention it is three-layer co-extruded go out polyvinylidene difluoride film preparation method enter according to the following steps
OK：
(1) internal layer, middle level are mixed respectively through high-speed mixer with outer layer raw material, mixing temperature is 15～60 DEG C, is mixed
300～1000rpm of rotating speed is closed, internal layer, middle level, outer layer compound is respectively obtained；(2) by internal layer, middle level, outer layer compound difference
Putting into double screw extruder carries out melting, disperses and extruding pelletization, respectively obtains internal layer, middle level and outer layer raw material particle,
Extrusion temperature is 120～240 DEG C, and screw speed is 200～500rpm；(3) internal layer, middle level and outer layer raw material particle are dried
Afterwards, put into respectively in three single-screw machine extruders of three-layer co-extruded slobbering machine or inflation film manufacturing machine, carry out conveying at 180～230 DEG C,
Fusing and extruding, and rack-style casting die head or screw type film-blowing die head are converged into, die head temperature is 210～230 DEG C, Jing die heads
Extrusion after-drawing, cooling and shaping, trimming winding, so as to obtain described three-layer co-extruded polyvinylidene difluoride film.
The present invention provide it is three-layer co-extruded go out polyvinylidene difluoride film and preparation method thereof compared with prior art, beneficial effect
It is really：The present invention it is three-layer co-extruded go out polyvinylidene difluoride film there is three-decker, internal layer is the blend of PVDF and PMMA,
PMMA substantially improves the adhesive property of PVDF, therefore thin film has good adhesive property, is conducive to thin film with guard block
Surface strong bond；Ultraviolet absorber and inorganic filler are contained in middle level, especially titanium dioxide, thus thin film effectively intercept it is ultraviolet
Line；Outer layer does not contain PMMA based on PVDF, with excellent weatherability and water vapor barrier property.
Description of the drawings
Fig. 1 be it is three-layer co-extruded go out polyvinylidene difluoride film structure schematic diagram.
In figure, 1- outer layers；2- middle levels；3- internal layers.
Specific embodiment
Referring to the drawings 1, it is three-layer co-extruded go out polyvinylidene difluoride film include 1 three layers of internal layer 3, middle level 2 and outer layer from bottom to top
Structure.The internal layer 3 is tack coat, and the middle level 2 is UV-blocking layer, and the outer layer 1 is PVDF layers.Inner layer sheet during use
Face is adhesive surface, outer layer and air contact.
Kynoar is the polyvinylidene fluoride homopolymer or copolymer prepared using suspension polymerization or emulsion polymerization,
The melt flow rate (MFR) (Melt Flow Rate, MFR) tested under 230 DEG C of temperature, load 5kg is 2～30g/10min.When
When Kynoar MFR is less than 2g/10min, application viscosity is too high, not easy processing, easily causes thin film became uneven；When poly- inclined
When fluorothene MFR is higher than 30g/10min, as Kynoar molecular weight is too low, the mechanical property of thin film is very poor.Preferably,
When the MFR of Kynoar is 6～25g/10min, thin film thickness is uniform, and mechanical property is qualified.
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 present embodiment provided it is a kind of three-layer co-extruded go out polyvinylidene difluoride film thickness be 10 microns, wherein：Internal layer 2 is micro-
Rice, 6 microns of middle level, 2 microns of outer layer.Internal layer raw material：90 parts of Kynoar, 10 parts of polymethyl methacrylate；Middle level raw material：
71.9 parts of Kynoar, 10 parts of polymethyl methacrylate, 15 parts of anatase thpe white powder, mean diameter are 0.02 micron, are resisted
Oxygen agent 1010 is respectively 0.05 part and 0.05 part with irgasfos 168 weight portion, benzotriazole ultraviolet absorber 2- (2- hydroxyls-
5- aminomethyl phenyls) 3 parts of-benzotriazole.Outer layer raw material：99.95 parts of Kynoar, 0.05 part of antioxidant 1076.
First, internal layer, middle level are mixed through high-speed mixer with outer layer raw material, mixing temperature is 15 DEG C, mixes rotating speed
300rpm；Then, compound is put into double screw extruder to be melted, disperseed and extruded pelletizing, respectively obtain internal layer, in
Layer and outer layer raw material particle, extrusion temperature is 120～240 DEG C, and screw speed is 500rpm.Then, by dried internal layer,
Middle level is put in three-layer co-extruded slobbering machine respectively with outer layer raw material particle, is conveyed, melted and is extruded at 180～230 DEG C,
And rack-style casting die head is converged into, die head temperature is 230 DEG C, the extrusion after-drawing of Jing die heads, cooling and shaping, trimming winding, from
And the three-layer co-extruded polyvinylidene difluoride film A required for obtaining.
Embodiment 2
The present embodiment provided it is a kind of three-layer co-extruded go out polyvinylidene difluoride film thickness be 25 microns, wherein：Internal layer 5 is micro-
Rice, 15 microns of middle level, 5 microns of outer layer.Internal layer raw material：65 parts of Kynoar, 35 parts of polymethyl methacrylate；Middle level is former
Material：63 parts of Kynoar, 15 parts of polymethyl methacrylate, 20 parts of Rutile type titanium dioxide, antioxidant are 1,098 0.05
Part, combination of the ultraviolet absorber for salicylic acid esters and benzophenone class, double acid double phenol A ester and 2,2 '-dihydroxy -4,4 '-two
Methoxy benzophenone is divided into 0.75 part with 0.75 part；Outer layer raw material：99.95 parts of Kynoar, anti-oxidant DLTP 0.05
Part.
First, internal layer, middle level are mixed through high-speed mixer with outer layer raw material, mixing temperature is 60 DEG C, mixes rotating speed
650rpm；Then, compound is put into double screw extruder to be melted, disperseed and extruded pelletizing, respectively obtain internal layer, in
Layer and outer layer raw material particle, extrusion temperature is 120～240 DEG C, and screw speed is 500rpm.Then, by dried internal layer,
Middle level is put in three-layer co-extruded slobbering machine respectively with outer layer raw material particle, is conveyed, melted and is extruded at 180～230 DEG C,
And rack-style casting die head is converged into, die head temperature is 210 DEG C, the extrusion after-drawing of Jing die heads, cooling and shaping, trimming winding, from
And the three-layer co-extruded polyvinylidene difluoride film B required for obtaining.
Embodiment 3
The present embodiment provided it is a kind of three-layer co-extruded go out polyvinylidene difluoride film thickness be 50 microns, wherein：Internal layer 10
Micron, 30 microns of middle level, 10 microns of outer layer.Internal layer raw material：65 parts of Kynoar, 35 parts of polymethyl methacrylate；Middle level
Raw material：73 parts of Kynoar, 10 parts of polymethyl methacrylate, anatase thpe white powder are respectively 10 parts and 5 parts with barium sulfate,
Antioxidant is 1,010 0.5 parts, benzotriazole ultraviolet absorber 2- (2 '-methyl -4 '-hydroxy phenyl)-benzotriazole and triazine
Class ultraviolet absorber 2,4- bis- chloro- 6- (4- morpholinyls) -1,3,5-triazines are respectively 1 part with 0.5 part.Outer layer raw material：Gather inclined fluorine
94.5 parts of ethylene, 5 parts of anatase thpe white powder, 0.5 part of antioxidant 1010.
First, internal layer, middle level are mixed through high-speed mixer with outer layer raw material, mixing temperature is 37.5 DEG C, and mixing turns
Fast 650rpm；Then, compound is put into double screw extruder to be melted, disperseed and extruded pelletizing, respectively obtain internal layer,
Middle level and outer layer raw material particle, extrusion temperature is 120～240 DEG C, and screw speed is 350rpm.Then, in will be dried
Layer, middle level and outer layer raw material particle are put in three single-screw machine extruders of inflation film manufacturing machine respectively, are carried out at 180～230 DEG C
Conveying, fusing and extruding, and screw type film-blowing die head is converged into, die head temperature is 210 DEG C, the extrusion after-drawing of Jing die heads, cooling
Sizing, trimming winding, so as to the three-layer co-extruded polyvinylidene difluoride film C required for obtaining.
Embodiment 4
The present embodiment provided it is a kind of three-layer co-extruded go out polyvinylidene difluoride film thickness be 100 microns, 20 microns of internal layer,
60 microns of middle level, 20 microns of outer layer.Internal layer raw material：40 parts of Kynoar, 60 parts of polymethyl methacrylate；Middle level raw material：
49.9 parts of Kynoar, 20 parts of polymethyl methacrylate, anatase thpe white powder are respectively 25 parts and 5 parts with Calcium Carbonate, resist
Oxygen agent is 1,010 0.05 parts, and benzotriazole ultraviolet absorber 2- (2 '-hydroxyl -5 '-tert-butyl-phenyl)-benzotriazole 0.05
Part.Outer layer raw material：89 parts of Kynoar, 10 parts of anatase thpe white powder, 1 part of antioxidant 1010.
First, internal layer, middle level are mixed through high-speed mixer with outer layer raw material, mixing temperature is 15 DEG C, mixes rotating speed
1000rpm；Then, compound is put into double screw extruder to be melted, disperseed and extruded pelletizing, respectively obtain internal layer,
Middle level and outer layer raw material particle, extrusion temperature is 120～240 DEG C, and screw speed is 350rpm.Then, in will be dried
Layer, middle level and outer layer raw material particle are put in three single-screw machine extruders of inflation film manufacturing machine respectively, are carried out at 180～230 DEG C
Conveying, fusing and extruding, and screw type film-blowing die head is converged into, die head temperature is 210 DEG C, the extrusion after-drawing of Jing die heads, cooling
Sizing, trimming winding, so as to the three-layer co-extruded polyvinylidene difluoride film D required for obtaining.
Embodiment 5
The present embodiment provided it is a kind of three-layer co-extruded go out polyvinylidene difluoride film thickness be 25 microns, wherein：Internal layer 5 is micro-
Rice, 15 microns of middle level, 5 microns of outer layer.Internal layer raw material：90 parts of Kynoar, 10 parts of polymethyl methacrylate；Middle level is former
Material：96 parts of Kynoar, antioxidant are 164 1 parts, benzotriazole ultraviolet absorber 2- (2- hydroxy-5-methyl base phenyl)-
3 parts of benzotriazole.Outer layer raw material：99.95 parts of Kynoar, 0.05 part of antioxidant 264.
First, internal layer, middle level are mixed through high-speed mixer with outer layer raw material, mixing temperature is 15 DEG C, mixes rotating speed
1000rpm；Then, compound is put into double screw extruder to be melted, disperseed and extruded pelletizing, respectively obtain internal layer,
Middle level and outer layer raw material particle, extrusion temperature is 120～240 DEG C, and screw speed is 200rpm.Then, in will be dried
Layer, middle level and outer layer raw material particle are put in three-layer co-extruded slobbering machine respectively, conveyed, melted and are squeezed at 180～230 DEG C
Pressure, and rack-style casting die head is converged into, die head temperature is 230 DEG C, the extrusion after-drawing of Jing die heads, cooling and shaping, trimming winding,
So as to the three-layer co-extruded polyvinylidene difluoride film E required for obtaining.
Surveyed using method of testing of the polyvinylidene difluoride film in solar photovoltaic cell backplane film with PET base material plate cohesive force
The cohesive force of three-layer co-extruded polyvinylidene fluoride film A-E samples prepared by examination embodiment 1～5.While the vapor to film sample
The aging post yellowing index of transmitance, ultraviolet irradiation is tested, and control sample is conventional 25 microns of monolayer polyvinylidene difluoride films,
Test result is summarized in following table：
Test result shows：The preparation of the present invention it is three-layer co-extruded go out polyvinylidene difluoride film, the adhesive property of internal layer is excellent
In monofilm, with bigger cohesive force；Middle level ultraviolet-resistant layer can effectively intercept ultra-vioket radiation, the ultraviolet spokes of trilamellar membrane Jing
Illumination aging post yellowing index is significantly less than monofilm, therefore trilamellar membrane anti-ultraviolet ageing performance is better than monofilm.As outer layer is
PVDF layers, play a part of to intercept steam, and trilamellar membrane water vapour permeability is significantly lower than monofilm.
Claims (10)
1. it is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film, it is characterised in that：The thin film from bottom to top successively by internal layer, in
Layer, outer layer three-decker composition, the internal layer are tack coat, and the middle level is UV-blocking layer, and the outer layer is PVDF layers.
2. it is according to claim 1 it is three-layer co-extruded go out polyvinylidene difluoride film, it is characterised in that：The thickness of the internal layer is
2～20 microns, the thickness in the middle level is 6～60 microns, and the thickness of the outer layer is 2～20 microns.
3. it is according to claim 1 it is three-layer co-extruded go out polyvinylidene difluoride film, it is characterised in that：The internal layer includes following
The raw material of mass parts：40～90 parts of Kynoar；10～60 parts of polymethyl methacrylate.
4. it is according to claim 1 it is three-layer co-extruded go out polyvinylidene difluoride film, it is characterised in that：The middle level includes following
The raw material of mass parts：49.9～96 parts of Kynoar；0.05～1 part of antioxidant A；0.05～3 part of ultraviolet absorber.
5. it is as claimed in claim 4 it is three-layer co-extruded go out polyvinylidene difluoride film, it is characterised in that the raw material in the middle level is matched somebody with somebody
Fang Wei：
Middle layer formula ()：49.9～96 parts of Kynoar；0.05～1 part of antioxidant A；0.05～3 part of ultraviolet absorber；
Middle layer formula (two)：49.9～96 parts of Kynoar；0.05～1 part of antioxidant A；0.05～3 part of ultraviolet absorber；
0.1～20 part of polymethyl methacrylate；
Middle layer formula (three)：49.9～96 parts of Kynoar；0.05～1 part of antioxidant A；0.05～3 part of ultraviolet absorber；
0.1～30 part of white inorganic filler A
49.9～96 parts of middle layer formula (four) Kynoar；0.05～1 part of antioxidant A；0.05～3 part of ultraviolet absorber；It is poly-
0.1～20 part of methyl methacrylate；0.1～30 part of white inorganic filler A.
6. it is according to claim 1 it is three-layer co-extruded go out polyvinylidene difluoride film, it is characterised in that：The outer layer includes following
The raw material of mass parts：89～99.95 parts of Kynoar；0.05～1 part of antioxidant B.
7. it is according to claim 6 it is three-layer co-extruded go out polyvinylidene difluoride film, it is characterised in that the formula of the outer layer is：
89～99.95 parts of outer layer formula () Kynoar；0.05～1 part of antioxidant B；
89～99.95 parts of outer layer formula (two) Kynoar；0.1～10 part of white inorganic filler B；Antioxidant B 0.05～1
Part.
8. according to one of claim 3～7 it is three-layer co-extruded go out polyvinylidene difluoride film, it is characterised in that：It is described poly- inclined
Fluorothene is the polyvinylidene fluoride homopolymer or copolymer prepared using suspension polymerization or emulsion polymerization, 230 DEG C of temperature,
The melt flow rate (MFR) tested under load 5kg is 2～30g/10min；The polymethyl methacrylate is in 230 DEG C of temperature, load
The melt flow rate (MFR) tested under lotus 5kg is 2～30g/10min.
9. according to one of claim 4～7 it is three-layer co-extruded go out polyvinylidene difluoride film, it is characterised in that：The antioxygen
Agent A or B be independently each phenolic antioxidant, organic phosphates antioxidant, one or more mixed in sulphur ester antioxidant
Close；White inorganic the filler A or B each stand alone as Rutile type titanium dioxide, anatase thpe white powder, barium sulfate, lithopone, carbon
One or more mixing in sour calcium, Pulvis Talci, silicon dioxide, calcium oxide, aluminium hydroxide, magnesium hydroxide, aluminium oxide
Thing；The ultraviolet absorber is salicylic acid esters, benzophenone class, benzotriazole, group-substituted acrylonitrile, triazines and hindered amines
One or more mixture in ultraviolet absorber.
10. it is according to claim 1 it is three-layer co-extruded go out polyvinylidene difluoride film, it is characterised in that：Described is three-layer co-extruded
Go out polyvinylidene difluoride film to be obtained by the following method：(1) internal layer, middle level and outer layer raw material are mixed respectively through high-speed mixer
Close, respectively obtain internal layer, middle level, outer layer compound；(2) internal layer, middle level, outer layer compound are put into into twin-screw extrusion respectively
Machine is carried out melting, is disperseed and extruding pelletization, respectively obtains internal layer, middle level and outer layer raw material particle；(3) by internal layer, middle level with
After outer layer raw material particle is dried, put in three single-screw machine extruders of three-layer co-extruded slobbering machine or inflation film manufacturing machine respectively,
180～230 DEG C are conveyed, melted and are extruded, and converge into rack-style casting die head or screw type film-blowing die head, die head temperature
For 210～230 DEG C, Jing die heads extrude after-drawing, cooling and shaping, trimming winding, so as to obtain the three-layer co-extruded polyvinylidene fluoride
Alkene thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610830875.3A CN106541656A (en) | 2016-09-19 | 2016-09-19 | It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610830875.3A CN106541656A (en) | 2016-09-19 | 2016-09-19 | It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106541656A true CN106541656A (en) | 2017-03-29 |
Family
ID=58367848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610830875.3A Pending CN106541656A (en) | 2016-09-19 | 2016-09-19 | It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106541656A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107554019A (en) * | 2017-08-22 | 2018-01-09 | 嘉兴市高正高分子材料有限公司 | It is a kind of it is three-layer co-extruded go out polyethylene film and preparation method thereof |
| CN108116018A (en) * | 2017-12-15 | 2018-06-05 | 东华大学 | A kind of anti-scribble engineering thermoplastic material plate and its preparation and application |
| CN109148632A (en) * | 2018-07-20 | 2019-01-04 | 杭州福禧新材料有限公司 | A kind of three-decker co-extrusion solar cell backboard and preparation method thereof containing PBT |
| CN109367146A (en) * | 2018-08-29 | 2019-02-22 | 绍兴福膜新材料有限公司 | A kind of extra-weather-proof protecting solar cell film and preparation method thereof |
| CN110294907A (en) * | 2018-03-23 | 2019-10-01 | 深圳市一心电子有限公司 | Backboard membrane used for solar batteries and preparation method thereof |
| CN110643291A (en) * | 2018-06-26 | 2020-01-03 | 上海海优威新材料股份有限公司 | Adhesive film having irradiation-treated inner layer and method for producing same |
| CN110643290A (en) * | 2018-06-26 | 2020-01-03 | 上海海优威新材料股份有限公司 | Weather-resistant adhesive film and preparation method thereof |
| CN112606500A (en) * | 2019-12-30 | 2021-04-06 | 武汉高正新材料科技有限公司 | Easy-to-adhere architectural decoration film |
| CN113291010A (en) * | 2021-05-13 | 2021-08-24 | 日氟荣高分子材料(上海)有限公司 | Maintenance-free transparent film, preparation method and application thereof |
| CN113400610A (en) * | 2021-05-31 | 2021-09-17 | 天津新兴东方临近空间航天科技有限公司 | Multilayer co-extrusion film process for fluorine-containing resin high-performance helium barrier film |
| CN113524825A (en) * | 2021-07-21 | 2021-10-22 | 天津新兴东方临近空间航天科技有限公司 | Blow molding process of multilayer co-extruded film of fluorine-containing resin for infrared hot air balloon |
| CN115401969A (en) * | 2022-08-12 | 2022-11-29 | 中天光伏材料有限公司 | Front film material and photovoltaic module |
| NL2029984A (en) * | 2021-12-01 | 2023-01-26 | Jiaxing Gaozheng New Material Tech Co Ltd | Pvdf membrane and preparation device and method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080311406A1 (en) * | 2005-12-06 | 2008-12-18 | Arkema France | (Ligno) Cellulose Material Board Coated with a Pmma and Pvdf-Based film |
| CN102157591A (en) * | 2011-01-11 | 2011-08-17 | 山东东岳高分子材料有限公司 | Back panel of solar cell and preparation method thereof |
| CN104191770A (en) * | 2014-09-17 | 2014-12-10 | 上海海优威新材料股份有限公司 | Polyvinylidene fluoride composite membrane and preparation method thereof |
| CN104842617A (en) * | 2015-05-18 | 2015-08-19 | 中天科技精密材料有限公司 | High-water-vapor-barrier polyvinylidene fluoride film and preparation method thereof |
| CN105196633A (en) * | 2015-10-15 | 2015-12-30 | 浙江歌瑞新材料有限公司 | Decorative film adopting PP (polypropylene) substrate |
| CN206510542U (en) * | 2016-09-19 | 2017-09-22 | 浙江凯阳新材料股份有限公司 | It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film |
-
2016
- 2016-09-19 CN CN201610830875.3A patent/CN106541656A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080311406A1 (en) * | 2005-12-06 | 2008-12-18 | Arkema France | (Ligno) Cellulose Material Board Coated with a Pmma and Pvdf-Based film |
| CN102157591A (en) * | 2011-01-11 | 2011-08-17 | 山东东岳高分子材料有限公司 | Back panel of solar cell and preparation method thereof |
| CN104191770A (en) * | 2014-09-17 | 2014-12-10 | 上海海优威新材料股份有限公司 | Polyvinylidene fluoride composite membrane and preparation method thereof |
| CN104842617A (en) * | 2015-05-18 | 2015-08-19 | 中天科技精密材料有限公司 | High-water-vapor-barrier polyvinylidene fluoride film and preparation method thereof |
| CN105196633A (en) * | 2015-10-15 | 2015-12-30 | 浙江歌瑞新材料有限公司 | Decorative film adopting PP (polypropylene) substrate |
| CN206510542U (en) * | 2016-09-19 | 2017-09-22 | 浙江凯阳新材料股份有限公司 | It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film |
Non-Patent Citations (3)
| Title |
|---|
| 吕世光: "《塑料助剂手册》", 31 March 1986, 轻工业出版社 * |
| 周殿明: "《塑料薄膜挤出成型》", 30 April 2012, 机械工业出版社 * |
| 黄棋尤: "《塑料包装薄膜——生产·性能·应用》", 31 March 2003, 机械工业出版社 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107554019A (en) * | 2017-08-22 | 2018-01-09 | 嘉兴市高正高分子材料有限公司 | It is a kind of it is three-layer co-extruded go out polyethylene film and preparation method thereof |
| CN108116018A (en) * | 2017-12-15 | 2018-06-05 | 东华大学 | A kind of anti-scribble engineering thermoplastic material plate and its preparation and application |
| CN110294907A (en) * | 2018-03-23 | 2019-10-01 | 深圳市一心电子有限公司 | Backboard membrane used for solar batteries and preparation method thereof |
| CN110643290A (en) * | 2018-06-26 | 2020-01-03 | 上海海优威新材料股份有限公司 | Weather-resistant adhesive film and preparation method thereof |
| CN110643291A (en) * | 2018-06-26 | 2020-01-03 | 上海海优威新材料股份有限公司 | Adhesive film having irradiation-treated inner layer and method for producing same |
| CN109148632A (en) * | 2018-07-20 | 2019-01-04 | 杭州福禧新材料有限公司 | A kind of three-decker co-extrusion solar cell backboard and preparation method thereof containing PBT |
| CN109367146A (en) * | 2018-08-29 | 2019-02-22 | 绍兴福膜新材料有限公司 | A kind of extra-weather-proof protecting solar cell film and preparation method thereof |
| CN112606500A (en) * | 2019-12-30 | 2021-04-06 | 武汉高正新材料科技有限公司 | Easy-to-adhere architectural decoration film |
| CN113291010A (en) * | 2021-05-13 | 2021-08-24 | 日氟荣高分子材料(上海)有限公司 | Maintenance-free transparent film, preparation method and application thereof |
| CN113291010B (en) * | 2021-05-13 | 2024-01-19 | 日氟荣高分子材料(上海)有限公司 | Maintenance-free transparent film, preparation method and application thereof |
| CN113400610A (en) * | 2021-05-31 | 2021-09-17 | 天津新兴东方临近空间航天科技有限公司 | Multilayer co-extrusion film process for fluorine-containing resin high-performance helium barrier film |
| CN113524825A (en) * | 2021-07-21 | 2021-10-22 | 天津新兴东方临近空间航天科技有限公司 | Blow molding process of multilayer co-extruded film of fluorine-containing resin for infrared hot air balloon |
| NL2029984A (en) * | 2021-12-01 | 2023-01-26 | Jiaxing Gaozheng New Material Tech Co Ltd | Pvdf membrane and preparation device and method |
| CN115401969A (en) * | 2022-08-12 | 2022-11-29 | 中天光伏材料有限公司 | Front film material and photovoltaic module |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106541656A (en) | It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film and preparation method thereof | |
| CN106366519A (en) | Polyvinylidene fluoride thin film and preparing method thereof | |
| CN104497929B (en) | A kind of special binding resin of aluminium-plastic panel and preparation method thereof | |
| US20110212318A1 (en) | Nanoscale ir absorbers in multilayer moldings | |
| CN103182821B (en) | A kind of modified polyamide laminated film and preparation method thereof | |
| CN1539549A (en) | Laminated multiporous polylefin film and its prepn. metod | |
| US11173693B2 (en) | Vinylidene fluoride-based resin multi-layered film | |
| CN206510542U (en) | It is a kind of it is three-layer co-extruded go out polyvinylidene difluoride film | |
| JP6882897B2 (en) | Polyester film containing amorphous polyester | |
| SK285992B6 (en) | Method for manufacturing single layer films | |
| JP6784075B2 (en) | Laminated film | |
| TWI461438B (en) | Film based on fluoropolymer and on zinc oxide without acrylic odour for photovoltaic application | |
| CN103311342A (en) | Solar cell back panel film and preparation method thereof | |
| US20120135256A1 (en) | Process Of Manufacturing Film Containing EVOH | |
| CN1836884A (en) | Method for manufacturing oriented plastic film | |
| CN108485159A (en) | A kind of preparation method of the low saturating polyolefin film raw material of water of high temperature resistant | |
| KR20160068760A (en) | Co-extruded multi-layer polyester films having hydrolytic stability and improved delamination resistance | |
| CN110920185A (en) | High-barrier puncture-resistant irradiation-resistant crosslinked multilayer heat shrinkable film and preparation method thereof | |
| KR20130141521A (en) | Fluoropolymer-based film for photovoltaic application | |
| CN111875947B (en) | Modified polyketone resin and preparation method thereof, nylon composite film and preparation method and application thereof | |
| CN105176071B (en) | A kind of floride-free two layers of co-extrusion photovoltaic back and preparation method thereof | |
| CN107554019A (en) | It is a kind of it is three-layer co-extruded go out polyethylene film and preparation method thereof | |
| CN104842617A (en) | High-water-vapor-barrier polyvinylidene fluoride film and preparation method thereof | |
| CN103101268A (en) | Frosted polyvinylidene fluoride film and preparation method thereof | |
| CN206553441U (en) | A kind of polyvinylidene difluoride film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170329 |
|
| RJ01 | Rejection of invention patent application after publication |