CN107501815A - A kind of scratch-resistant polyvinylidene difluoride film of high water resistant and preparation method thereof - Google Patents
A kind of scratch-resistant polyvinylidene difluoride film of high water resistant and preparation method thereof Download PDFInfo
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- 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
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- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention discloses scratch-resistant polyvinylidene difluoride film of a kind of high water resistant and preparation method thereof, belong to solar-energy photo-voltaic cell application field, curtain coating or blown film are made after being mixed by following components：Kynoar, organically-modified laminar nano inorganic compound, plasticized modifier, inorganic ultraviolet light screener, scratch resistance liniment, processing aid and heat stabilizer.Organically-modified laminar nano inorganic compound improvement in the present invention prepares the water vapor barrier property of film；Plasticized modifier causes film to have good toughness；Inorganic ultraviolet light screener can reflect or absorb ultraviolet, ensure the high ultraviolet-resistant rate of film；Scratch resistance liniment significantly reduces the coefficient of friction of film surface, significantly improves scraping and wiping resistance performance；Processing aid improves the mobility of Kynoar, is easy to carry out melting extrusion and film forming.Polyvinylidene difluoride film prepared by the present invention has the advantages that excellent mechanical property, water vapor rejection characteristic, scratch resistance and high-weatherability.
Description
Technical field
The present invention relates to scratch-resistant polyvinylidene difluoride film of a kind of high water resistant and preparation method thereof, belong to photovoltaic
Battery applications field.
Background technology
Solar cell is a kind of device that luminous energy is converted into electric energy, is reply energy shortage and environmental pollution
Important sharp weapon.The working environment of solar cell is mostly open air, and high humidity is perishable, while can be by various boisterous
Infringement, therefore the encapsulation of solar cell can directly affect its service life.Battery back-sheet is located at the outermost layer of module backside,
Solar cell module is protected not corroded by steam under outdoor environment, it is the anti-oxidation of blocking oxygen, high-low temperature resistant, good exhausted
Edge and ageing-resistant performance, decay resistance.Common backboard typically has three-decker：Internal layer be polyethylene (PE) film or
Fluorine-containing coat；Intermediate layer is polyethylene terephthalate (PET) film of biaxial tension；Outer layer is fluorine film, including poly- fluorine
Ethene (PVF), Kynoar (PVDF) or other fluorine materials.
Kynoar is a kind of fluorine material of excellent performance, has the resistant to chemical etching of protrusion, weatherability, resistance to height
Warm and excellent electrical insulating property, therefore it is highly suitable as photovoltaic back diaphragm.But its surface energy is low, with the material such as PET
Adhesive property it is poor, thus often it is modified using acrylic polymer, improves cementitiousness to reach, improves and can process
The purpose of performance.At present, the Kynar films of the Arkema companies at most used in China and the Tedlar films of E.I.Du Pont Company, all
It is the fluorine film of the material based on fluoro containing polymerses/acrylate polymer.
Because PMMA heat endurances, water vapor rejection characteristic etc. are not so good as PVDF, hence in so that PVDF/ acrylic ester polymerizations
Thing film turns into the part that water-resisting ability is most weak during backboard respectively forms.Due to backboard water-resisting ability influence component generating efficiency with
And service life, thus it is extremely urgent to develop the fluorine film with high water resistant characteristic.
Further, since the manufacture of fluorine film, film when backboard is laminating and terminal box is Nian Jie with being inevitably present artificial behaviour
Make, so as to bring film cut scratch equivalent damage, and this damage is in addition to giving visual perception's impact, it is also possible to
Influence barrier property of the film to ultraviolet light, steam etc..
The content of the invention
The technical problems to be solved by the invention are to develop to have high water resistant characteristic, while have the sun of scratch-resistant characteristic concurrently
Can battery back-sheet protection fluorine film.
The present invention also provides the preparation method of above-mentioned solar energy backboard membrane.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of scratch-resistant polyvinylidene difluoride film of high water resistant, described scratch-resistant polyvinylidene difluoride film by under following by weight
Blown film or curtain coating form after the component mixing of part meter：69.9~87.4 parts of Kynoar, organically-modified laminar nano is inorganic
2~6 parts of compound, 8~15 parts of plasticized modifier, 1~15 part of inorganic ultraviolet light screener, 1~5 part of scratch resistance liniment, processing
0.1~2 part of 0.5~5 part of auxiliary agent and heat stabilizer.
In the technical program, the organically-modified laminar nano inorganic compound in the present invention make use of laminated inorganic matter
Nano-lamellar structure and its orientation, the barrier property of film can be effectively improved；Plasticized modifier is advantageous to film holding
Good toughness, significantly improve the impact resistance and elongation at break of film；Inorganic ultraviolet light screener can largely obstruct purple
Outside line, protect base material and back veneer material；Scratch resistance liniment can lubricious polymeric thing surface, significantly reduce film surface coefficient of friction,
So that film has outstanding scraping and wiping resistance performance；Processing aid improves the mobility of Kynoar, is easy to carry out melting extrusion
It is molded with processing film；Heat stabilizer can prevent or delay the heat ageing of formula.Polyvinylidene difluoride film tool prepared by the present invention
There are excellent mechanical property, water vapor rejection characteristic, scratch resistance and high-weatherability.
Preferably, the organically-modified laminar nano inorganic compound, which is modified intercalator processing, has nanometer
The inorganic compound of layer structure, can be the phyllosilicate, flake graphite and layered metal oxide of orgnic-intercalation modification
In one or more of combinations.Wherein the phyllosilicate of orgnic-intercalation modification can be：Talcum, the cloud of orgnic-intercalation modification
Female and clay (kaolin, montmorillonite and marlstone) etc.；Layered metal oxide can be：Vanadic anhydride, molybdenum sesquioxide
With tungstic acid etc..The organically-modified laminar nano inorganic compound has big radius-thickness ratio, when its be dispersed in it is poly-
In compound matrix, iris action can be played so that the diffusion motion of gas or liquid small molecule in polymeric matrix must be around
These lamellas are crossed, gas is considerably increased, the active path that fluid molecule spreads in polymeric matrix, substantially increases polymerization
The barrier property of thing material for gaseous and liquid.The interlayer of laminar nano inorganic compound contains substantial amounts of inorganic ions, has
Higher hydrophily.Therefore, in the preparation process of the organic composite material of laminar nano inorganic compound to laminar nano without
Machine compound, which carries out organic-treating, makes a very crucial step.By organic-treating, it is set to be changed into oleophylic by hydrophily
Property, polymer molecular chain can easily be intercalation into nm inorganic compound interlayer.
Preferably, described plasticized modifier is the esters of acrylic acid or methyl acrylic ester bullet for having core shell structure
One or more of combinations in property body.
Preferably, the inorganic ultraviolet light screener is titanium dioxide, zinc oxide, barium sulfate, zinc sulphide, pigment charcoal
One or more of combinations in black, kaolin, talcum powder, calcium carbonate and In The Mixed Metal Oxide Pigments, wherein titanium dioxide,
Zinc oxide, barium sulfate, zinc sulphide, kaolin, talcum powder, the average grain diameter of calcium carbonate and In The Mixed Metal Oxide Pigments are 0.2
~3 microns, the primary particle diameter of colour carbon black is 8~70 nanometers.
Preferably, described scratch resistance liniment is small molecule acid amides series lubricant agent, ptfe micropowder and organic poly- silicon
One or more of combinations in oxygen alkane.
Preferably, described processing aid is one or more of combinations in acrylic class.Adding used in the present invention
Work auxiliary agent is one or more of combinations in acrylic class, can be Rhom and Hass's Paraloid products, including
K120p, K125p, K175p, K130p etc.；MIT's Metblen products；Japanese Zhong Yuan chemical industrial companies Kane
Ace products etc..
Preferably, described heat stabilizer is one or more of combinations in organic tin, metal soap.Wherein,
The heat stabilizer of organic tin can be：Dibutyl tin laurate, maleic acid dioctyltin, double (butyl maleates) two
Fourth tin, double (lauryl mercaptan) dibutyl tins, S, S '-bis- (the thio different pungent tin of Glycolic acid) dibutyl tin, tin dilaurate two are just pungent
Ji Xi etc.；The heat stabilizer of metal soap can be：Calcium stearate, magnesium stearate, lithium stearate, zinc stearate, aluminum stearate,
Double stearic acid aluminium, calcium laurate, zinc laurate, ricinoleic acid calcium, 2 ethyl hexanoic acid zinc etc..
A kind of preparation method of the scratch-resistant polyvinylidene difluoride film of described high water resistant, this method comprise the following steps：
1) feed components are well mixed by the first step with high-speed mixer, obtain Kynoar mixture, high-speed mixer
Rotating speed be 500~1500rpm, mixing temperature control is at 30-60 DEG C, incorporation time 10-60min；
2) second step obtains being film-made special particle, extrusion by double screw extruder to Kynoar mixture extruding pelletization
At 180~250 DEG C, screw speed controls in 200~450rpm temperature control；
3) Kynoar special particle is cast or Blown Film.
Further, step 3) detailed process is as follows：Using single or multiple lift casting machine, 180~260 DEG C of extrusion temperature,
Screw speed is 30~120rpm, and curtain coating head temperature is 190~240 DEG C, and the film of extrusion cools and solidifies through chill roll, then
Winding winding, you can prepare polyvinylidene difluoride film；Or using single or multiple lift inflation film manufacturing machine, 180~260 DEG C of extrusion temperature,
Screw speed is 30~80rpm, and blown-film die temperature is 190~240 DEG C, and the film that blown film obtains is after cooling and shaping through cuing open
Side, then winding winding, you can prepare polyvinylidene difluoride film.
The beneficial effects of the invention are as follows：By the effect of organically-modified laminar nano inorganic compound, significantly improve
The water vapor rejection characteristic of polyvinylidene difluoride film, greatly prolong the generating efficiency and service life of component；It is meanwhile resistance in formula
The roughness that liniment greatly reduces film surface is scraped, enhances the scraping and wiping resistance performance of film.
Embodiment
Below by specific embodiment, technical scheme is described in further detail.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, and used equipment and raw material etc. are equal
For commercially available prod.Method in following embodiments, it is the conventional method of this area unless otherwise instructed.
Embodiment 1-6
The formula of the scratch-resistant polyvinylidene difluoride film of high water resistant is referring to table 1.The raw material used in each embodiment is as follows：
1st, Kynoar (PVDF)：Trade name is PVDF DS206, and supplier is that Shandong divine boat of China new material science and technology is limited
Company, melt index are that (test condition is 20g/10min：230 DEG C, 5kg).
2nd, organically-modified laminar nano inorganic compound is that modified intercalator processing has nanometer laminated structure
Inorganic compound, can be orgnic-intercalation modification phyllosilicate, flake graphite and layered metal oxide in one kind or
Several combinations.Wherein the phyllosilicate of orgnic-intercalation modification can be：Talcum, mica and the clay of orgnic-intercalation modification
(kaolin, montmorillonite and marlstone) etc.；Layered metal oxide can be：Vanadic anhydride, molybdenum sesquioxide and three oxidations
Tungsten etc..
For example, the nano imvite of orgnic-intercalation modification, trade name DK1N, supplier are：Zhejiang Feng Hong new material stocks
Part Co., Ltd.
3rd, plasticized modifier is that have one kind in the esters of acrylic acid or methyl acrylic ester elastomer of core shell structure
Or several combination.
For example, trade name：Metablen S-2001, supplier are：Mitsubishi Li Yang Co., Ltd..
4th, inorganic ultraviolet light screener be titanium dioxide, zinc oxide, barium sulfate, zinc sulphide, colour carbon black, kaolin,
One or more of combinations in talcum powder, calcium carbonate and In The Mixed Metal Oxide Pigments, wherein titanium dioxide, zinc oxide, sulphur
Sour barium, zinc sulphide, kaolin, talcum powder, the average grain diameter of calcium carbonate and In The Mixed Metal Oxide Pigments are 0.2~3 micron, color
The primary particle diameter of plain carbon black is 8~70 nanometers.
For example, colour carbon black, trade name：Elftex 570, supplier are：Cabot (chemical industry) Tianjin Co., Ltd.
5th, scratch resistance liniment be small molecule acid amides series lubricant agent, ptfe micropowder and one kind in organopolysiloxane or
Several combinations.
For example, trade name：Tegomer H-Si 6440P, supplier are limited to win wound Degussa Specialty Chemical (Shanghai)
Company.
6th, processing aid is one or more of combinations in acrylic class.Processing aid used in the present invention is acrylic
One or more of combinations in class, can be Rhom and Hass's Paraloid products, including K120p, K125p, K175p,
K130p etc.；MIT's Metblen products；Japanese Zhong Yuan chemical industrial companies Kane Ace products etc..
For example, one of which processing aid trade name is：P551A, supplier are that beautiful positive (Nantong) macromolecule of Mitsubishi is limited
Company；Another auxiliary agent trade name is Acrylic K-355P, and supplier is：Dow Chemical company.
7th, heat stabilizer is one or more of combinations in organic tin, metal soap.Wherein, the heat of organic tin is steady
Determining agent can be：Dibutyl tin laurate, maleic acid dioctyltin, double (butyl maleates) two fourth tin, double (lauryls
Mercaptan) dibutyl tin, S, S '-bis- (the thio different pungent tin of Glycolic acid) dibutyl tin, Bis(lauroyloxy)dioctyltin etc.；Metal soap
Heat stabilizer can be：Calcium stearate, magnesium stearate, lithium stearate, zinc stearate, aluminum stearate, double stearic acid aluminium, bay
Sour calcium, zinc laurate, ricinoleic acid calcium, 2 ethyl hexanoic acid zinc etc..
For example, heat stabilizer is a kind of organic tin stabilizer and a kind of combination of metal soap stabilizer, wherein：It is organic
Tin stabilizer is dibutyitin maleate (DBTM), and supplier is：AKZO companies of Sweden；Metal soap stabilizer is stearic acid
Calcium, supplier are：Shandong Zibo Zichuan foundation oil chemistry factory.The synergy of the combination of heat stabilizer is ratio in PVC industry
More universal, the emphasis to be studied of non-invention, tired state is not done herein.
Table 1 (parts by weight)
Polyvinylidene difluoride film is prepared by the formula in table 1 and following step：
Feed components are subjected to mechanical mixture, using high-speed mixer, mixed 10~60 minutes at normal temperatures, high-speed mixer
Rotating speed be 500~1500rpm, mixing temperature is controlled at 30~60 DEG C；
Well mixed ground mixture is subjected to melting extrusion granulation, using double screw extruder, extrusion temperature is 180~250 DEG C,
Screw speed is 200~450rpm, 4.5~8MPa of head pressure, you can obtains PVDF thin film PP Pipe Compound particle.
By PP Pipe Compound particle casting film-forming, using individual layer casting machine, 180~260 DEG C of extrusion temperature, screw speed is 30~
120rpm, curtain coating head temperature are 190~240 DEG C.The film of extrusion cools and solidifies through chill roll, then winding winding, you can
Obtain PVDF thin film.
The process can also be：Using single or multiple lift inflation film manufacturing machine, 180~260 DEG C of extrusion temperature, screw speed is 30~
80rpm, blown-film die temperature are 190~240 DEG C, and through cuing open side after cooling and shaping, then winding is wound the film for being blow molded to obtain,
Polyvinylidene difluoride film can be prepared.
In embodiment 1~6, the film of 25 micron thickness is made, then the drawing of test product polyvinylidene difluoride film
Stretch the Key Performance Indicators such as intensity, water vapour permeability, weatherability and percent thermal shrinkage.Test result is as shown in table 2.
The performance test results of the embodiment 1~6 of table 2 and comparative example
Various embodiments above formula is easy to twin-screw extrusion and film forming.Comparative example is low-resistance water, the formula of low scratch resistance,
Organically-modified laminar nano inorganic compound and scratch resistance liniment are not added.By the comparison of comparative example and embodiment 1~6,
Illustrate that the polyvinylidene difluoride film water vapour permeability of the present invention is very low, and with good mechanical property, excellent resistance to old
Change performance and scraping and wiping resistance performance, fully meet the requirement of solar photovoltaic cell backplane.
Embodiment described above is a kind of preferred version of the present invention, not makees any formal limit to the present invention
System, there are other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (10)
1. the scratch-resistant polyvinylidene difluoride film of a kind of high water resistant, it is characterised in that described is scratch-resistant polyvinylidene difluoride film
Formed by blown film after following component mixing by weight or curtain coating：69.9~87.4 parts of Kynoar, it is organically-modified
2~6 parts of laminar nano inorganic compound, 8~15 parts of plasticized modifier, 1~15 part of inorganic ultraviolet light screener, scratch resistance liniment
1~5 part, 0.1~2 part of 0.5~5 part of processing aid and heat stabilizer.
2. the scratch-resistant polyvinylidene difluoride film of a kind of high water resistant according to claim 1, it is characterised in that described poly- inclined
PVF molecular weight is 20~1,000,000.
3. the scratch-resistant polyvinylidene difluoride film of a kind of high water resistant according to claim 1, it is characterised in that described organic
Modified laminar nano inorganic compound is the inorganic compound with nanometer laminated structure of modified intercalator processing, can be with
Be orgnic-intercalation modification phyllosilicate, flake graphite and layered metal oxide in one or more of combinations.
A kind of 4. scratch-resistant polyvinylidene difluoride film of high water resistant according to claim 1, it is characterised in that the toughness reinforcing
Modifying agent is that have one or more of combinations in the esters of acrylic acid or methyl acrylic ester elastomer of core shell structure.
5. the scratch-resistant polyvinylidene difluoride film of a kind of high water resistant according to claim 1, it is characterised in that described inorganic
Class ultraviolet light screener be titanium dioxide, zinc oxide, barium sulfate, zinc sulphide, colour carbon black, kaolin, talcum powder, calcium carbonate and
Any of In The Mixed Metal Oxide Pigments or several combinations, wherein titanium dioxide, zinc oxide, barium sulfate, zinc sulphide, height
Ridge soil, talcum powder, the average grain diameter of calcium carbonate and In The Mixed Metal Oxide Pigments are 0.2~3 micron, the bioblast of colour carbon black
Footpath is 8~70 nanometers.
A kind of 6. scratch-resistant polyvinylidene difluoride film of high water resistant according to claim 1, it is characterised in that the scratch resistance
Liniment is any of small molecule acid amides series lubricant agent, ptfe micropowder and organopolysiloxane or several combinations.
A kind of 7. scratch-resistant polyvinylidene difluoride film of high water resistant according to claim 1, it is characterised in that the processing
Auxiliary agent is one or more of combinations in acrylic class.
8. the scratch-resistant polyvinylidene difluoride film of a kind of high water resistant according to claim 1, it is characterised in that the heat is steady
Agent is determined for one or more of combinations in organic tin, metal soap.
A kind of 9. preparation method of the scratch-resistant polyvinylidene difluoride film of the high water resistant described in claim 1, it is characterised in that institute
Preparation method method is stated to comprise the following steps：
1) feed components are well mixed by the first step with high-speed mixer, obtain Kynoar mixture, high-speed mixer
Rotating speed be 500~1500rpm, mixing temperature control is at 30-60 DEG C, incorporation time 10-60min；
2) second step obtains being film-made special particle, extrusion by double screw extruder to Kynoar mixture extruding pelletization
At 180~250 DEG C, screw speed controls in 200~450rpm temperature control；
3) Kynoar special particle is cast or Blown Film.
10. a kind of preparation method of the scratch-resistant polyvinylidene difluoride film of high water resistant according to claim 9, its feature exist
In step 3) is：With single or multiple lift casting machine, 180~260 DEG C of extrusion temperature, screw speed is 30~120rpm, casting machine
Head temperature is 190~240 DEG C, and the film of extrusion cools and solidifies through chill roll, then winding winding, you can prepares Kynoar
Film；Or using single or multiple lift inflation film manufacturing machine, 180~260 DEG C of extrusion temperature, screw speed is 30~80rpm, inflation film manufacturing machine
Head temperature is 190~240 DEG C, and through cuing open side after cooling and shaping, then winding is wound the film that blown film obtains, you can is prepared poly- inclined
Fluoroethylene film.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715685A (en) * | 2018-06-15 | 2018-10-30 | 广州市瑞合新材料科技有限公司 | Low permeability rate add-on type liquid silicon rubber and preparation method thereof |
| CN109550770A (en) * | 2018-11-23 | 2019-04-02 | 浙江晶科能源有限公司 | A kind of method and apparatus for scrapping photovoltaic back harmless treatment |
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| CN109550770A (en) * | 2018-11-23 | 2019-04-02 | 浙江晶科能源有限公司 | A kind of method and apparatus for scrapping photovoltaic back harmless treatment |
| CN110128767A (en) * | 2019-05-09 | 2019-08-16 | 常州回天新材料有限公司 | The low transparent polyvinylidene fluoride film and its manufacturing method that high ultraviolet-resistant is precipitated |
| CN113459547A (en) * | 2021-05-27 | 2021-10-01 | 日氟荣高分子材料(上海)有限公司 | Surface-grafted fluorine membrane and preparation method thereof |
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