CN102796334A - Flame-retardant polyvinylidene fluoride film and preparation method thereof - Google Patents
Flame-retardant polyvinylidene fluoride film and preparation method thereof Download PDFInfo
- Publication number
- CN102796334A CN102796334A CN2012103359036A CN201210335903A CN102796334A CN 102796334 A CN102796334 A CN 102796334A CN 2012103359036 A CN2012103359036 A CN 2012103359036A CN 201210335903 A CN201210335903 A CN 201210335903A CN 102796334 A CN102796334 A CN 102796334A
- Authority
- CN
- China
- Prior art keywords
- retardant
- film
- fire
- preparation
- weight
- 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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a flame-retardant polyvinylidene fluoride film and a preparation method thereof, belonging to the technical field of plastic films. The flame-retardant polyvinylidene fluoride film comprises the following components in parts by weight: 59-81 parts of polyvinylidene fluoride resin, 5-17 parts of filler, 9-20 parts of reinforced resin, 0.2-1 part of heat stabilizer, 1-17 parts of and 0.1-2 parts of coupling agent. The flame-retardant polyvinylidene fluoride film is prepared by an extrusion casting process. The polyvinylidene fluoride weather-resistant film provided by the invention has the advantages of high flatness, favorable mechanical properties and low film shrinkage; and the addition of the flame retardant improves the flame retardancy of the composite system. The polyvinylidene fluoride film can be used on a packaging material back panel of a solar photovoltaic battery pack.
Description
Technical field
The present invention relates to a kind of fire-retardant polyvinylidene difluoride film and preparation method thereof, this polyvinylidene difluoride film improves to some extent at aspects such as flame retardant properties, mechanical property and planarizations.The present invention adopts salivation method to be equipped with fire-retardant polyvinylidene difluoride film.
Background technology
Pvdf (PVDF) resin mainly is meant the multipolymer of vinylidene fluoride homopolymer or vinylidene and other a small amount of fluorine-containing vinyl monomers.The mass content of fluorine atom is between 59～60% among the PVDF, and texture ratio is more regular.The maximum electronegativity energy of fluorine atom makes that the fluorine carbon bond that forms is very firm, adds the unique symplex structure of its molecule, makes PVDF have excellent outdoor weatherability and erosion resistance, fabulous antifouling property and anti-permeability performance.Simultaneously, the tensile strength of PVDF resin is high, and temperature tolerance, wear resistance and creep resistance are good.PVDF uses very extensively as anticorrosion, insulation, weatherable materials, is mainly used in aspects such as chemical plant, electric, the energy, environmental protection and trade sales coating, has become the second largest kind that is only second to polytetrafluoroethylene (PTFE) in the fluoro-resin at present.
Solar cell was outdoor life-time service at least 25 years; Boisterous test such as stand to expose to the weather, drench with rain; Require very high to its packaged material; Not only require to have weathering resistance, ultra-violet radiation resisting and the very excellent chemicalstability of excellence, and require to have excellent electric insulation performance and lower water vapour, oxygen permeability.The plastics film of employing single variety can't satisfy the requirement of above-mentioned harshness at all.At present, using maximum is the backboard with PVDF film and the bonding compound preparation of PET film, can satisfy the encapsulation requirement of the outdoor life-time service of solar photovoltaic battery component.Along with developing rapidly of solar-energy photo-voltaic cell, the demand of PVDF film is increasing.
The fusing point of pure PVDF resin and decomposition temperature differ more than 140 ℃, but after mineral fillers such as interpolation titanium oxide, its decomposition temperature declines to a great extent, and the degraded easily that becomes causes processing difficulties.The film forming properties of PVDF film is poor in addition, needs other resins of interpolation and auxiliary agent to improve.The precision of prescription, complete processing and membrane equipment etc. are very big to influences such as the processing characteristics of PVDF film, film forming properties, mechanical property, composite performances.At present, have only several companies can produce polyvinylidene difluoride film in the world, mainly concentrate on America and Europe, Japan and Korea S, mainly adopt blow moulding or hydrostomia method.For example, the Arkema company of France adopts blow moulding.Companies such as Korea S SKC adopt the hydrostomia method.Two kinds of methods comparatively speaking, though the film cross direction tear strength that salivation method is equipped with is lower, its planarization is better than blown film method, is easy to bond with other films be compounded to form multilayered structure.
The flame retardant properties of PVDF self is relatively good, and limiting oxygen index(LOI) is 42～44, and is higher than airborne oxygen level, so in air, can put out certainly.But processing characteristics and the film forming properties in order to improve PVDF needs to add other resins, filler, auxiliary agent etc. and carries out modification, thereby have influence on the incendivity of material usually.In addition, for some application or when having cost requirement to need PVDF film very thin (≤30 μ m), its flame retardant properties also descends greatly, is difficult to reach UL94 VTM-0 level.This just need improve the flame retardant properties of PVDF co-mixing system through the interpolation fire retardant.In order to reduce fire retardant, need be optimized prescription and complete processing from many-sides such as fire retardant kind and consumption, addition manner, blend processing modes to PVDF co-mixing system Effect on Performance.
Summary of the invention
The present invention is some problems that still exist in polyvinylidene difluoride film production and the use in order to solve; A kind of fire-retardant polyvinylidene difluoride film and preparation method thereof is provided; This fire-retardant polyvinylidene difluoride film is to obtain fully by extruding salivation method, improves to some extent at aspects such as flame retardant properties, mechanical property and planarizations.
Be to realize above-mentioned purpose, the technical scheme that the present invention taked is: described fire-retardant polyvinylidene difluoride film, and the raw material and the component concentration that it is characterized in that being used to preparing this film are following:
Polyvinylidene fluoride resin 59～81 weight parts
Filler 5～17 weight parts
Strengthen resin 9～20 weight parts
Thermo-stabilizer 0.2～1 weight part
Fire retardant 1～17 weight part
Coupling agent 0.1～2 weight part
Further, polyvinylidene fluoride resin according to the invention, its index is a weight-average molecular weight, weight-average molecular weight is between 20～1,000,000.
Further, filler according to the invention is any one or any several kinds combination in titanium oxide, lime carbonate, silicon-dioxide or the talcum powder.The median size of said filler is less than 1 micron.
Further, enhancing resin according to the invention is the one or more combination in esters of acrylic acid or the methyl acrylic ester resin, and its index is a weight-average molecular weight, and weight-average molecular weight is between 5～200,000.
Further, thermo-stabilizer according to the invention is any one or any several kinds of combinations in Hinered phenols, phosphorous acid esters, the organic tin.
Further, fire retardant according to the invention is any one or any several kinds of combinations in white lake, Marinco H, phosphoric acid ester, sulphonate, sulfonamides or the melamine class.
Further, coupling agent according to the invention is any one in silane coupling agent, titanate coupling agent or the aluminium titanium composite coupler.
In addition, other additives such as toughner, photostabilizer, lubricant, organic or inorganic pigment and dyestuff be introduced in the composition of raw materials of the present invention.
The preparation method of a kind of fire-retardant polyvinylidene difluoride film of the present invention is following:
(1) uses high-speed mixer with raw material uniform mixing such as polyvinylidene fluoride resin, filler, enhancing resin, thermo-stabilizer, fire retardant and coupling agents, obtain compound; The high-speed mixer stir speed (S.S.) is 500～1500rpm, and churning time is 5～20 minutes;
(2) use then twin screw extruder to the described compound of step (1) carry, plasticizing, blend granulation, obtain the granulation material; The length-to-diameter ratio of dual-screw-stem machine forcing machine is 40～52, extrude processing temperature is that 200～245 ℃, screw speed are 200～400rpm;
(3) then the described granulation material adding of step (2) is extruded in the slobbering machine, extrude hydrostomia; The online Corona Surface Treatment of carrying out; Extrusion temperature is that 200～245 ℃, screw speed are that 20～100rpm, hydrostomia head temperature are that 200～250 ℃, packaging film feeding speed are 5～50m/min; At last to film cut edge, rolling can obtain polyvinylidene difluoride film;
The melting index of the said granulation material of above-mentioned steps among the present invention (2) is 5～30g/10min (230 ℃, load 5kg).
The thickness of the said fire-retardant polyvinylidene difluoride film of above-mentioned steps among the present invention (3) is 15～50 microns.
Compared with prior art, the invention has the beneficial effects as follows:
The polyvinylidene difluoride film of the present invention preparation has excellent weathering resistance, ultraviolet aging resistance property and mechanical property, and good flame retardancy is even film thickness during less than 30 microns, still can reach UL94 VTM-0 level.Can satisfy the encapsulation requirement of solar components, use as the backboard outermost layer; And can be applicable to fields such as electronics and building.Granulation material of the present invention has good flowability and thermostability; Filler and auxiliary agent are uniformly dispersed in resin, machine-shaping at a lower temperature, and also melt strength is high; Be fit to very much extrude curtain coating technology, obtain very easily that planarization is good, the polyvinylidene difluoride film of thickness homogeneous.
Embodiment
Following embodiment further specifies of the present invention, and the present invention is not limited to following examples and implementation method.
The raw material of using among the embodiment is following:
Polyvinylidene fluoride resin (PVDF): trade mark SOLEF 1001, U.S. Solvay company
Filler: titanium oxide (TiO
2), trade mark R-103, du pont company
Strengthen resin: polymethylmethacrylate (PMMA), trade mark SR6350, company of Japanese Asahi Chemical Industry
Thermo-stabilizer: trade mark Irganox 1076, BASF Aktiengesellschaft
Fire retardant: super fine magnesium hydroxide Mg (OH) 2, the fire-retardant novel material of section ltd in the Hefei
Resorcinol biphosphonate RDP, Zhejiang Province Wansheng Chemical Co., Ltd
Coupling agent: trade mark NDZ-105, NanJing Shuguang Chemical Group Co., Ltd.
The composition of raw materials of Comparative Examples and embodiment is listed in the table 1, and each component concentration calculates according to weight percent.
Table 1 Comparative Examples and embodiment composition of raw materials table
| Material name | Comparative Examples | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| PVDF | 74.5 | 62 | 59 | 65.5 |
| TiO 2 | 10 | 10 | 10 | 10 |
| PMMA | 15 | 15 | 20 | 15 |
| Irganox 1076 | 0.5 | 0.5 | 0.5 | 0.5 |
| Mg(OH)2 | 0 | 8 | 0 | 0 |
| RDP | 0 | 4 | 10 | 8 |
| NDZ-105 | 0 | 0.5 | 0.5 | 1 |
Following Comparative Examples is prepared 100 kilograms of blended material with each embodiment respectively according to prescription shown in the table 1, uses forcing machine extruding pelletization material then, is equipped with polyvinylidene difluoride film with extruding hydrostomia mechanism at last, and concrete preparation method and step are seen Comparative Examples and embodiment.
Comparative Examples
The concrete preparation method and the step of polyvinylidene difluoride film are following:
(1) various raw materials is joined respectively in the high-speed mixer in proportion,, obtain compound through uniform mixing.The high-speed mixer stir speed (S.S.) is 800rpm, and mixing time is 15 minutes;
(2) then the main spout of compound from twin screw extruder added,, obtain the granulation material through conveying, plasticizing, blend granulation.The length-to-diameter ratio of dual-screw-stem machine forcing machine is 40, extrude processing temperature is that 230 ℃, screw speed are 300 rev/mins.The melting index of the granulation material that obtains is 9.5g/10min (230 ℃, load 5kg);
(3) then the described granulation material of step (2) is added slobbering machine, extrude hydrostomia.During hydrostomia, the online Corona Surface Treatment of carrying out; Extrusion temperature is 240 ℃, and screw speed is made as 20rpm, and the hydrostomia head temperature is made as 245 ℃, and packaging film feeding speed is made as 19m/min.Final online to film cut edge, rolling, prepare smooth polyvinylidene difluoride film.
Embodiment 1
The concrete preparation method and the step of polyvinylidene difluoride film are following:
(1) various raw materials is joined respectively in the high-speed mixer in proportion,, obtain compound through uniform mixing.The high-speed mixer stir speed (S.S.) is 1000rpm, and mixing time is 10 minutes;
(2) then the main spout of compound from twin screw extruder added,, obtain the granulation material through conveying, plasticizing, blend granulation.The length-to-diameter ratio of dual-screw-stem machine forcing machine is 40, extrude processing temperature is that 230 ℃, screw speed are 300 rev/mins.The melting index of the granulation material that obtains is 11.2g/10min (230 ℃, load 5kg);
(3) then the described granulation material of step (2) is added slobbering machine, extrude hydrostomia.During hydrostomia, the online Corona Surface Treatment of carrying out; Extrusion temperature is 240 ℃, and screw speed is made as 20rpm, and the hydrostomia head temperature is made as 245 ℃, and packaging film feeding speed is made as 20m/min.Final online to film cut edge, rolling, prepare smooth polyvinylidene difluoride film.
Embodiment 2
The concrete preparation method and the step of polyvinylidene difluoride film are following:
(1) the various raw materials except RDP is rendered to respectively in the high-speed mixer in proportion,, obtained compound through uniform mixing.The high-speed mixer stir speed (S.S.) is 800rpm, and mixing time is 15 minutes.
(2) then the main spout of compound from twin screw extruder added, RDP is added from forcing machine the 4th district with the liquid feeder.Compound is carried, plasticizing, blend granulation, obtains the granulation material.The length-to-diameter ratio of dual-screw-stem machine forcing machine is 40, extrude processing temperature is that 230 ℃, screw speed are 400rpm.The granulation material melting index that obtains is 17.9g/10min (230 ℃, load 5kg).
(3) then the described granulation material of step (2) is added slobbering machine, extrude hydrostomia.During hydrostomia, the online Corona Surface Treatment of carrying out; Extrusion temperature is made as 230 ℃, screw speed and is made as 50rpm, hydrostomia head temperature and is made as 235 ℃, packaging film feeding speed and is made as 35m/min.To film cut edge, rolling, prepare smooth polyvinylidene difluoride film.
Embodiment 3
The concrete preparation method and the step of polyvinylidene difluoride film are following:
(1) various raw materials is joined respectively in the high-speed mixer in proportion,, obtain compound through uniform mixing.The high-speed mixer stir speed (S.S.) is 1000rpm, and mixing time is 15 minutes;
(2) then the main spout of compound from twin screw extruder added,, obtain the granulation material through conveying, plasticizing, blend granulation.The length-to-diameter ratio of dual-screw-stem machine forcing machine is 40, extrude processing temperature is that 230 ℃, screw speed are 300 rev/mins.The melting index of the granulation material that obtains is 15.6g/10min (230 ℃, load 5kg);
(3) then the described granulation material of step (2) is added slobbering machine, extrude hydrostomia.During hydrostomia, the online Corona Surface Treatment of carrying out; Extrusion temperature is 235 ℃, and screw speed is made as 20rpm, and the hydrostomia head temperature is made as 240 ℃, and packaging film feeding speed is made as 27m/min.Final online to film cut edge, rolling, prepare smooth polyvinylidene difluoride film.
Comparative Examples and the polyvinylidene difluoride film that each embodiment prepares were placed more than 48 hours, carried out the test of various performances again.Test result is seen table 2.
Table 2 film performance test data sheet
Annotate: "/" expression fails to reach VTM-0 in the table 2.
The polyvinylidene difluoride film surfacing for preparing among the embodiment, non-wrinkled, stain is few.As shown in table 2, film has the good mechanical performance, and 150 ℃ of following percent thermal shrinkages are lower, and single thin film is excellent to the barrier property of water vapour simultaneously; In addition, the adding of fire retardant obviously improves the film flame retardant properties, still can reach the VTM-0 level when film thickness is 28 microns.The adding of coupling agent has improved the dispersion of white titanium pigment in resin, has improved the tensile strength of film.It is thus clear that the fire-retardant polyvinylidene difluoride film of the present invention's preparation can satisfy the requirement of solar photovoltaic battery component encapsulation back veneer material, also can be applied to industries such as electronics and building simultaneously.
Claims (8)
1. fire-retardant polyvinylidene difluoride film and preparation method thereof, it is characterized in that: comprise pvdf, filler, enhancing resin, thermo-stabilizer, fire retardant and coupling agent, the proportioning of percentage ratio meter is following by weight:
Polyvinylidene fluoride resin 59～81 weight parts
Filler 5～17 weight parts
Strengthen resin 9～20 weight parts
Thermo-stabilizer 0.2～1 weight part
Fire retardant 1～17 weight part
Coupling agent 0.1～2 weight part.
2. a kind of fire-retardant polyvinylidene difluoride film as claimed in claim 1 and preparation method thereof is characterized in that said polyvinylidene fluoride resin, and its index is a weight-average molecular weight, and weight-average molecular weight is between 20～1,000,000.
3. a kind of fire-retardant polyvinylidene difluoride film as claimed in claim 1 and preparation method thereof; It is characterized in that said filler is any one or any several kinds combination in titanium oxide, lime carbonate, silicon-dioxide or the talcum powder, the median size of said filler is less than 1 micron.
4. a kind of fire-retardant polyvinylidene difluoride film as claimed in claim 1 and preparation method thereof; It is characterized in that said enhancing resin is the one or more combination in esters of acrylic acid or the methyl acrylic ester resin; Its index is a weight-average molecular weight, and weight-average molecular weight is between 5～200,000.
5. a kind of fire-retardant polyvinylidene difluoride film as claimed in claim 1 and preparation method thereof is characterized in that said thermo-stabilizer is any one or any several kinds of combinations in Hinered phenols, phosphorous acid esters, the organic tin.
6. a kind of fire-retardant polyvinylidene difluoride film as claimed in claim 1 and preparation method thereof is characterized in that said fire retardant is any one or any several kinds of combinations in white lake, Marinco H, phosphoric acid ester, sulphonate, sulfonamides or the melamine class.
7. a kind of fire-retardant polyvinylidene difluoride film as claimed in claim 1 and preparation method thereof is characterized in that said coupling agent is any one in silane coupling agent, titanate coupling agent or the aluminium titanium composite coupler.
8. a kind of fire-retardant polyvinylidene difluoride film as claimed in claim 1 and preparation method thereof is characterized in that the preparation method of film is following:
(1) uses high-speed mixer with raw material uniform mixing such as polyvinylidene fluoride resin, filler, enhancing resin, thermo-stabilizer, fire retardant and coupling agents, obtain compound; The high-speed mixer stir speed (S.S.) is 500～1500rpm, and churning time is 5～20 minutes;
(2) use then twin screw extruder to the described compound of step (1) carry, plasticizing, blend granulation, obtain the granulation material; The length-to-diameter ratio of dual-screw-stem machine forcing machine is 40～52, extrude processing temperature is that 200～245 ℃, screw speed are 200～400rpm;
(3) then the described granulation material adding of step (2) is extruded in the slobbering machine, extrude hydrostomia; The online Corona Surface Treatment of carrying out; Extrusion temperature is that 200～245 ℃, screw speed are that 20～100rpm, hydrostomia head temperature are that 200～250 ℃, packaging film feeding speed are 5～50m/min; At last to film cut edge, rolling can obtain polyvinylidene difluoride film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103359036A CN102796334A (en) | 2012-09-12 | 2012-09-12 | Flame-retardant polyvinylidene fluoride film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103359036A CN102796334A (en) | 2012-09-12 | 2012-09-12 | Flame-retardant polyvinylidene fluoride film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102796334A true CN102796334A (en) | 2012-11-28 |
Family
ID=47195655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103359036A Pending CN102796334A (en) | 2012-09-12 | 2012-09-12 | Flame-retardant polyvinylidene fluoride film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102796334A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744862A (en) * | 2013-12-31 | 2015-07-01 | 江苏昊华光伏科技有限公司 | PVDF (Polyvinylidene Fluoride) sheet material |
| CN106009427A (en) * | 2016-07-20 | 2016-10-12 | 郑泓 | Special material for white polyvinylidene fluoride cast film |
| CN107815045A (en) * | 2017-10-13 | 2018-03-20 | 乳源东阳光氟树脂有限公司 | A kind of wearability polyvinylidene difluoride film |
| CN108172653A (en) * | 2018-01-19 | 2018-06-15 | 中天科技精密材料有限公司 | A kind of PVDF thin film of high reflectance and preparation method thereof, application |
| CN108285599A (en) * | 2018-02-05 | 2018-07-17 | 常州回天新材料有限公司 | A method of it recycling waste and old pvdf membrane and manufactures terminal box raw material |
| CN109560165A (en) * | 2018-11-14 | 2019-04-02 | 宁波高新区州致科技有限公司 | A kind of composite membrane used for solar batteries and preparation method thereof |
| CN109776920A (en) * | 2019-01-23 | 2019-05-21 | 上海邦中新材料有限公司 | A kind of flame-proof polyethylene packaging film and preparation method thereof |
| CN111688157A (en) * | 2020-05-29 | 2020-09-22 | 芜湖航天特种电缆厂股份有限公司 | Ethernet abrasion-resistant protective layer and preparation method thereof |
| CN113754973A (en) * | 2021-09-10 | 2021-12-07 | 宁波肯倍知行机器人设备制造有限公司 | Novel molecular material for robot |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101495562A (en) * | 2006-08-04 | 2009-07-29 | 阿科玛法国公司 | Photovoltaic modules having a polyvinylidene fluoride surface |
| CN101681946A (en) * | 2007-06-15 | 2010-03-24 | 阿科玛股份有限公司 | photovoltaic modules having a polyvinylidene fluoride backsheet |
| CN102311595A (en) * | 2010-07-02 | 2012-01-11 | 沈辉 | Fluorine-containing membrane applied to photovoltaic industry |
| CN102336992A (en) * | 2010-07-19 | 2012-02-01 | 刘波 | Preparation method of special material for fluorine-containing plastic film |
| CN102432963A (en) * | 2011-08-17 | 2012-05-02 | 常州荣晟新材料科技有限公司 | Fluorinated weather-resistant film for solar photovoltaic battery back plate and preparation method of fluorinated weather-resistant film |
| CN102649309A (en) * | 2011-02-23 | 2012-08-29 | 北京化工大学 | Polyvinylidene fluoride composite membrane prepared through multilayer coextrusion tape casting method |
-
2012
- 2012-09-12 CN CN2012103359036A patent/CN102796334A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101495562A (en) * | 2006-08-04 | 2009-07-29 | 阿科玛法国公司 | Photovoltaic modules having a polyvinylidene fluoride surface |
| CN101681946A (en) * | 2007-06-15 | 2010-03-24 | 阿科玛股份有限公司 | photovoltaic modules having a polyvinylidene fluoride backsheet |
| CN102311595A (en) * | 2010-07-02 | 2012-01-11 | 沈辉 | Fluorine-containing membrane applied to photovoltaic industry |
| CN102336992A (en) * | 2010-07-19 | 2012-02-01 | 刘波 | Preparation method of special material for fluorine-containing plastic film |
| CN102649309A (en) * | 2011-02-23 | 2012-08-29 | 北京化工大学 | Polyvinylidene fluoride composite membrane prepared through multilayer coextrusion tape casting method |
| CN102432963A (en) * | 2011-08-17 | 2012-05-02 | 常州荣晟新材料科技有限公司 | Fluorinated weather-resistant film for solar photovoltaic battery back plate and preparation method of fluorinated weather-resistant film |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744862A (en) * | 2013-12-31 | 2015-07-01 | 江苏昊华光伏科技有限公司 | PVDF (Polyvinylidene Fluoride) sheet material |
| CN106009427A (en) * | 2016-07-20 | 2016-10-12 | 郑泓 | Special material for white polyvinylidene fluoride cast film |
| CN107815045A (en) * | 2017-10-13 | 2018-03-20 | 乳源东阳光氟树脂有限公司 | A kind of wearability polyvinylidene difluoride film |
| CN108172653A (en) * | 2018-01-19 | 2018-06-15 | 中天科技精密材料有限公司 | A kind of PVDF thin film of high reflectance and preparation method thereof, application |
| CN108285599A (en) * | 2018-02-05 | 2018-07-17 | 常州回天新材料有限公司 | A method of it recycling waste and old pvdf membrane and manufactures terminal box raw material |
| CN109560165A (en) * | 2018-11-14 | 2019-04-02 | 宁波高新区州致科技有限公司 | A kind of composite membrane used for solar batteries and preparation method thereof |
| CN109776920A (en) * | 2019-01-23 | 2019-05-21 | 上海邦中新材料有限公司 | A kind of flame-proof polyethylene packaging film and preparation method thereof |
| CN111688157A (en) * | 2020-05-29 | 2020-09-22 | 芜湖航天特种电缆厂股份有限公司 | Ethernet abrasion-resistant protective layer and preparation method thereof |
| CN113754973A (en) * | 2021-09-10 | 2021-12-07 | 宁波肯倍知行机器人设备制造有限公司 | Novel molecular material for robot |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102796334A (en) | Flame-retardant polyvinylidene fluoride film and preparation method thereof | |
| CN102010554B (en) | Material special for polyvinylidene fluoride film | |
| CN109485965A (en) | A kind of solar cell backboard substrate and preparation method and solar cell backboard | |
| CN102336992A (en) | Preparation method of special material for fluorine-containing plastic film | |
| CN104327433A (en) | Preparation method of polyvinylidene fluoride-based thin film | |
| CN107383799B (en) | Special material for polybutylene terephthalate-polyvinylidene fluoride alloy | |
| CN106633771B (en) | A kind of Wear-resistant, high-temperature resistant fire-retardant film or sheet material and preparation method thereof | |
| CN107841029B (en) | High-weather-resistance PE (polyethylene) film for solar cell back plate | |
| CN102432963A (en) | Fluorinated weather-resistant film for solar photovoltaic battery back plate and preparation method of fluorinated weather-resistant film | |
| CN106280696B (en) | Thermosetting high-flame-retardant matte ink for PET (polyethylene terephthalate) substrate | |
| CN104725817A (en) | Environmentally-friendly flame-retardant reinforced impact-resistant PC composite material | |
| CN102746599B (en) | High-thermal-oxidation-stability polyvinylidene fluoride composition and preparation method thereof | |
| CN102408649B (en) | Modified polyvinylidene fluoride material used for solar cell protective films and preparation method thereof | |
| CN106117694B (en) | A kind of attapulgite activeness and quietness resists long-term ultraviolet ageing floating material masterbatch | |
| CN104693748A (en) | Flame-retardant modified PC/PBT alloy and preparation method thereof | |
| CN113683878B (en) | Spiral substituted polyolefin and preparation method thereof, and polycarbonate composition and preparation method thereof | |
| CN104861370A (en) | Flame-retardant antistatic polyethylene modified polyvinyl chloride tube | |
| CN101759967A (en) | Halogen-free warp-resistant PBT of excellent electrical properties and preparing technique thereof | |
| CN104861358A (en) | Nanometer kaolin modified polyvinyl chloride composite material | |
| CN114274639A (en) | Multilayer co-extrusion transparent high-impact-resistance antistatic polycarbonate composite material and preparation method thereof | |
| CN102850752B (en) | Preparation method of flame retardant SEBS modified polycarbonate alloy material | |
| CN106159010A (en) | High tensile PVDF solar energy backboard membrane | |
| CN104419165A (en) | Inorganic nano flame-retardant modified PC (poly carbonate) and preparation method thereof | |
| CN104693756A (en) | Toughened, weather-resistant and modified fame-retardant PC/PBT alloy | |
| CN104693746A (en) | Mineral reinforced PC/PBT modified alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121128 |