CN104059317A - High-concentration white master batch for polyvinylidene fluoride (PVDF) films and production method thereof - Google Patents

High-concentration white master batch for polyvinylidene fluoride (PVDF) films and production method thereof Download PDF

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Publication number
CN104059317A
CN104059317A CN201410254047.0A CN201410254047A CN104059317A CN 104059317 A CN104059317 A CN 104059317A CN 201410254047 A CN201410254047 A CN 201410254047A CN 104059317 A CN104059317 A CN 104059317A
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China
Prior art keywords
pvdf
film
polyvinylidene difluoride
pigment
white master
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CN201410254047.0A
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Chinese (zh)
Inventor
陈朝泉
郑昀
顾建华
吴梓新
张怡
揭元萍
张春雷
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Shanghai Huayi Group Corp
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Shanghai Huayi Group Corp
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Priority to CN201410254047.0A priority Critical patent/CN104059317A/en
Publication of CN104059317A publication Critical patent/CN104059317A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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
    • B29C2948/92514—Pressure
    • 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
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/92609—Dimensions
    • B29C2948/92647—Thickness
    • 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
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

Abstract

The invention relates to a high-concentration white master batch for polyvinylidene fluoride (PVDF) films and a production method thereof, and mainly solves the problems of lower pigment concentration, poor dispersity and lower covering power in the white master batch for PVDF films, and the problems of poor flowability and poor film-forming property under high-concentration pigment proportioning conditions in the prior art. The high-concentration white master batch for PVDF films comprises the following components in percentage by weight: 30-80% of white pigment, 5-35% of dispersing agent, 0.1-5% of pigment organic coating agent and 5-52% of PVDF resin. The technical scheme well solves the problems, and the production method can be used for producing the high-concentration white master batch for PVDF films.

Description

High density white master material and production method thereof for polyvinylidene difluoride film
Technical field
The present invention relates to a kind of polyvinylidene difluoride film high density white master material and production method thereof.
Background technology
Due to the hydrophobic character of fluoro-containing plastic polyvinylidene difluoride (PVDF) (PVDF) material self, the mineral dyes such as titanium dioxide are difficult to it compatible and dispersion therein well, therefore market only has several offshore companies to make and sell polyvinylidene difluoride (PVDF) (PVDF) white master batch, white pigment concentration is generally all in 30%, and expensive.But 25 microns of individual layer polyvinylidene difluoride (PVDF) (PVDF) film using in the compound backboard membrane of New Energy Industry solar cell field need to add and exceedes the effectively opacifying property of 15% white pigment guarantee film; What is more, in the multi-layer co-extruded polyvinylidene difluoride (PVDF) of novel high-quality (PVDF) thin film fabrication, needs especially interpolation to exceed 30% white pigment in the effective efficiency layer of 10-15 micron thickness.This just the mass property such as the consistency to polyvinylidene difluoride (PVDF) for film (PVDF) high density white master material product and product middle and high concentration pigment and resin, dispersiveness and good film-forming properties requirements at the higher level have been proposed.
A kind of reported the PVDF of preparation film PP Pipe Compound in patent CN102010554 method, in the method, the addition of inorganic nano-filler can only arrive 10% of total amount.In patent CN102516691, also report a kind of special white method of sun power backboard membrane of manufacturing, it is by adding polymethylmethacrylate or low-molecular-weight polyethylene wax/fluorine-containing active dispersion agent, increase the addition to 40% of inorganic titanium white powder, but owing to having added a large amount of low molecular weight polyethylene wax, the heat decomposition temperature of PVDF master batch is significantly reduced, this has improved the difficulty of casting film-forming, and film is prone to defect.
The present invention has solved the problems referred to above targetedly.
Summary of the invention
One of technical problem to be solved by this invention be polyvinylidene difluoride (PVDF) in prior art (PVDF) film white master material pigment concentration lower, dispersed poor, opacifying power is weak and high density pigment ratio condition current downflow, the poor problem of film-forming properties, and a kind of new polyvinylidene difluoride film high density white master material is provided.This masterbatch has advantages of that pigment concentration is high, good dispersity, strong covering power and high density pigment ratio condition current downflow, film-forming properties are splendid.Two of technical problem to be solved by this invention is to provide the production method of a kind of polyvinylidene difluoride film corresponding with one of technical solution problem high density white master material.
For one of addressing the above problem, the technical solution used in the present invention is as follows: a kind of polyvinylidene difluoride film high density white master material, comprises that weight fraction is 30～80% white pigment, 5～35% dispersion agent, 0.1～5% pigment organic coating agent and the polyvinylidene fluoride resin of 5-52%.
In technique scheme, preferably, described white pigment is at least one in Rutile type Titanium Dioxide, anatase thpe white powder, zinc oxide, calcium carbonate, barium sulfate, zinc sulfide white, talcum powder, and weight fraction is 30～60%.
In technique scheme, preferably, described dispersion agent is that polycondensate class, esters of acrylic acid, methyl acrylic ester, fatty acid ester, the molecular weight of polyprotonic acid and polyvalent alcohol is at least one in 1～1,000,000 ester analog thermoplastic high molecular polymer, polyethylene wax, and weight fraction is 10～25%.
In technique scheme, preferably, the agent of described pigment organic coating is at least one in sodium laurylsulfonate, octadecanoic acid, stearin, titanic acid ester, silane, Aluminate, polyoxyethylene glycol, macrogol ester, and weight fraction is 1～4%.
In technique scheme, preferably, described polyvinylidene fluoride resin is at least one in the polyvinylidene fluoride resin of the polyvinylidene fluoride polyamino alkenyl resin of molecular weight between 10～2,000,000 or modification by copolymerization, and weight fraction is 10～45%.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the production method of high density white master material for a kind of polyvinylidene difluoride film, to comprise described white pigment, dispersion agent, the material of the agent of pigment organic coating and polyvinylidene fluoride resin adds in mixing tank according to described ratio or is directly fed and in twin screw extruder, carried out melt blending by feeding machine, twin screw extruder barrel zone temperature is 60～220 DEG C, screw speed is 50～200r/min, vacuum meter is with count-0.09～0MPa of gauge pressure, pass through screw rod shearing, mixing effect makes pigment in twin screw extruder, complete the molten organic coating of surperficial gas, and be dispersed in polyvinylidene fluoride resin with macromolecule dispersing agent, then carry out granulation, the dry polyvinylidene difluoride film high density white master material that makes.
In technique scheme, preferably, described twin screw extruder has vacuum pumping function.
The present invention is by adding the agent of pigment organic coating, polyvinylidene difluoride (PVDF) (PVDF) white master material of producing compared with prior art, has that pigment concentration is high, good dispersity, strong covering power and high density pigment ratio condition current downflow, a splendid feature of film-forming properties.Be specially adapted to require the solar cell backboard dedicated parent material that for film, polyvinylidene difluoride (PVDF) (PVDF) thin film fabrication is used of high opacifying property and ultrathin requirement, obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Prepare double centner polyvinylidene difluoride (PVDF) (PVDF) film high density white master material
1. each composition weight is:
2. preparation method
Join in multi-dimensional movement mixing machine disposable above-mentioned each constituent materials, mix 15 minutes, again the material mixing is sent in the twin screw extruder with vacuum pumping function, at extruder screw rotating speed 90r/min, 60～220 DEG C of machine barrel and die temperatures, under vacuum exhaust vacuum gauge pressure-0.05MPa condition, plasticate extrude, cooling, oven dry and pelletizing obtain 30% depth of shade that can be applicable to direct formation of film at surface, 1% thermal weight loss is greater than the polyvinylidene difluoride (PVDF) (PVDF) of 330 DEG C high dense white master material for film.
3. film-forming properties checking
The polyvinylidene difluoride (PVDF) of above-mentioned preparation (PVDF) film is directly dropped into high dense white master material in the sandwich layer forcing machine of three-layer co-extruded PVDF cast film production line of 1300mm fabric width and carries out the production of casting films masking, obtain the three-layer co-extruded cast film characteristic of industrialized polyvinylidene difluoride (PVDF) as follows:
Membrane structure Film total thickness Core layer thickness Transmittance Film aberration Do not disperse color dot
Three-decker 23μm 13μm 24％ Naked eyes have no Naked eyes have no
[embodiment 2]
Prepare double centner polyvinylidene difluoride (PVDF) (PVDF) film high density white master material
1. each composition weight is:
2. preparation method
First pigment coating is added in stirring mixer and mixed with macromolecule dispersing agent, again by its input in the automatic feeder with weigher, separately by pigment titanium white, pigment zinc oxide and barium sulfate mixture and PVDF resin are put into respectively the automatic feeder with weigher separately, set autofeed interlock speed in appeal formulation weight ratio, and in the double-screw extruding pelletizing machine of feeding with vacuum pumping function, at extruder screw rotating speed 200r/min, 60～220 DEG C of machine barrel and die temperatures, under vacuum exhaust vacuum gauge pressure-0.05MPa condition, plasticate and extrude, cooling, oven dry and pelletizing obtain 75% depth of shade, 1% thermal weight loss is greater than the polyvinylidene difluoride (PVDF) (PVDF) of 330 DEG C high dense white master material for film.
3. masking property verification
The individual layer PVDF that the polyvinylidene difluoride (PVDF) of embodiment 2 manufacturings (PVDF) high density white master material and commercially available pure polyvinylidene difluoride (PVDF) (PVDF) resin granular material are joined to fabric width 1600mm with the part by weight compounding of 1:4 extrudes in curtain coating film line forcing machine and is filmed production, obtains industrialized polyvinylidene difluoride (PVDF) individual layer cast film characteristic as follows:
Membrane structure Film thickness Transmittance Film aberration Do not disperse color dot
Single layer structure 25μm 21％ Naked eyes have no Naked eyes have no
[embodiment 3]
Prepare double centner polyvinylidene difluoride (PVDF) (PVDF) film high density white master material
1. each composition weight is:
2. preparation method
First pigment coating is added in stirring mixer and mixed with macromolecule dispersing agent, again by its input in the automatic feeder with weigher, separately by pigment titanium white, pigment zinc oxide and barium sulfate mixture and PVDF resin are put into respectively the automatic feeder with weigher separately, set autofeed interlock speed in appeal formulation weight ratio, and in the double-screw extruding pelletizing machine of feeding with vacuum pumping function, at extruder screw rotating speed 50r/min, 60～220 DEG C of machine barrel and die temperatures, under vacuum exhaust vacuum gauge pressure 0MPa condition, plasticate and extrude, cooling, oven dry and pelletizing obtain 80% depth of shade, 1% thermal weight loss is greater than the polyvinylidene difluoride (PVDF) (PVDF) of 330 DEG C high dense white master material for film.
3. masking property verification
The individual layer PVDF that the polyvinylidene difluoride (PVDF) of embodiment 3 manufacturings (PVDF) high density white master material and commercially available pure polyvinylidene difluoride (PVDF) (PVDF) resin granular material are joined to fabric width 1300mm with the part by weight compounding of 1:5 extrudes in curtain coating film line forcing machine and is filmed production, obtains industrialized polyvinylidene difluoride (PVDF) individual layer cast film characteristic as follows:
Membrane structure Film total thickness Transmittance Film aberration Do not disperse color dot
Single layer structure 25μm 21％ Naked eyes have no Naked eyes have no
[embodiment 4]
Prepare double centner polyvinylidene difluoride (PVDF) (PVDF) film high density white master material
1. each composition weight is:
2. preparation method
Join in multi-dimensional movement mixing machine disposable above-mentioned each constituent materials, mix 10 minutes, again the material mixing is sent in the twin screw extruder with vacuum pumping function, at extruder screw rotating speed 90r/min, 60～220 DEG C of machine barrel and die temperatures, under vacuum exhaust vacuum gauge pressure-0.09MPa condition, plasticate extrude, cooling, oven dry and pelletizing obtain 40% depth of shade 1% thermal weight loss that can be applicable to direct formation of film at surface and be greater than the polyvinylidene difluoride (PVDF) (PVDF) of 330 DEG C high dense white master material for film.
3. film-forming properties checking
The polyvinylidene difluoride (PVDF) of above-mentioned preparation (PVDF) film is directly dropped into high dense white master material in the sandwich layer forcing machine of three-layer co-extruded PVDF cast film production line of 1300mm fabric width and carries out the production of casting films masking, obtain the three-layer co-extruded cast film characteristic of industrialized polyvinylidene difluoride (PVDF) as follows:
Membrane structure Film total thickness Core layer thickness Transmittance Film aberration Do not disperse color dot
Three-decker 23μm 13μm 20％ Naked eyes have no Naked eyes have no
[embodiment 5]
Prepare double centner polyvinylidene difluoride (PVDF) (PVDF) film high density white master material
1. each composition weight is:
2. preparation method
Join in multi-dimensional movement mixing machine disposable above-mentioned each constituent materials, mix 10 minutes, again the material mixing is sent in the twin screw extruder with vacuum pumping function, at extruder screw rotating speed 90r/min, 60～220 DEG C of machine barrel and die temperatures, under vacuum exhaust vacuum gauge pressure-0.07MPa condition, plasticate extrude, cooling, oven dry and pelletizing obtain 60% depth of shade 1% thermal weight loss and be greater than the polyvinylidene difluoride (PVDF) (PVDF) of 300 DEG C high dense white master material for film.
3. film-forming properties checking
The polyvinylidene difluoride (PVDF) of above-mentioned preparation (PVDF) film is carried out to the production of casting films masking with dropping into after high dense white master material and commercially available pure polyvinylidene fluoride resin 1:1 compounding in the sandwich layer forcing machine of three-layer co-extruded PVDF cast film production line of 1300mm fabric width, obtains the three-layer co-extruded cast film characteristic of industrialized polyvinylidene difluoride (PVDF) as follows:
Membrane structure Film total thickness Core layer thickness Transmittance Film aberration Do not disperse color dot
Three-decker 26μm 15μm 22％ Naked eyes have no Naked eyes have no
[embodiment 6]
Prepare double centner polyvinylidene difluoride (PVDF) (PVDF) film high density white master material
1. each composition weight is:
2. preparation method
Join in multi-dimensional movement mixing machine disposable above-mentioned each constituent materials, mix 10 minutes, again the material mixing is sent in the twin screw extruder with vacuum pumping function, at extruder screw rotating speed 90r/min, 60～220 DEG C of machine barrel and die temperatures, under vacuum exhaust vacuum gauge pressure-0.07MPa condition, plasticate extrude, cooling, oven dry and pelletizing obtain 50% depth of shade 1% thermal weight loss that can be applicable to direct formation of film at surface and be greater than the polyvinylidene difluoride (PVDF) (PVDF) of 330 DEG C high dense white master material for film.
3. film-forming properties checking
The polyvinylidene difluoride (PVDF) of above-mentioned preparation (PVDF) film is carried out to the production of casting films masking with dropping into after high dense white master material and commercially available polyvinylidene fluoride resin 1:1 compounding in the individual layer PVDF cast film production line forcing machine of 1300mm fabric width, obtains industrialized polyvinylidene difluoride (PVDF) cast film characteristic as follows:
Membrane structure Film total thickness Transmittance Film aberration Do not disperse color dot
Single layer structure 25μm 20μm Naked eyes have no Naked eyes have no
[embodiment 7]
Prepare double centner polyvinylidene difluoride (PVDF) (PVDF) film high density white master material
1. each composition weight is:
2. preparation method
Join in multi-dimensional movement mixing machine disposable above-mentioned each constituent materials, mix 10 minutes, again the material mixing is sent in the twin screw extruder with vacuum pumping function, at extruder screw rotating speed 90r/min, 60～220 DEG C of machine barrel and die temperatures, under vacuum exhaust vacuum gauge pressure-0.07MPa condition, plasticate extrude, cooling, oven dry and pelletizing obtain and can 50% depth of shade 1% thermal weight loss be greater than the polyvinylidene difluoride (PVDF) (PVDF) of 330 DEG C high dense white master material for film.
3. film-forming properties checking
The polyvinylidene difluoride (PVDF) of above-mentioned preparation (PVDF) film is carried out to the production of casting films masking with dropping into after high dense white master material and commercially available polyvinylidene fluoride resin 1:2 compounding in the individual layer PVDF cast film production line forcing machine of 1300mm fabric width, obtains industrialized polyvinylidene difluoride (PVDF) individual layer cast film characteristic as follows:
Membrane structure Film total thickness Transmittance Film aberration Do not disperse color dot
Single layer structure 25μm 21％ Naked eyes have no Naked eyes have no
[embodiment 8]
Prepare double centner polyvinylidene difluoride (PVDF) (PVDF) film high density white master material
1. each composition weight is:
2. preparation method
Join in multi-dimensional movement mixing machine disposable above-mentioned each constituent materials, mix 10 minutes, again the material mixing is sent in the twin screw extruder with vacuum pumping function, at extruder screw rotating speed 90r/min, 60～220 DEG C of machine barrel and die temperatures, under vacuum exhaust vacuum gauge pressure-0.07MPa condition, plasticate extrude, cooling, oven dry and pelletizing obtain 30% depth of shade 1% thermal weight loss that can be applicable to direct formation of film at surface and be greater than the polyvinylidene difluoride (PVDF) (PVDF) of 320 DEG C high dense white master material for film.
3. film-forming properties checking
The polyvinylidene difluoride (PVDF) of above-mentioned preparation (PVDF) film is directly dropped into high dense white master material in the sandwich layer forcing machine of three-layer co-extruded PVDF cast film production line of 1300mm fabric width and carries out the production of casting films masking, obtain the three-layer co-extruded cast film characteristic of industrialized polyvinylidene difluoride (PVDF) as follows:
Membrane structure Film total thickness Core layer thickness Transmittance Film aberration Do not disperse color dot
Three layers 24μm 14μm 21％ Naked eyes have no Naked eyes have no
[embodiment 9]
Prepare double centner polyvinylidene difluoride (PVDF) (PVDF) film high density white master material
1. each composition weight is:
2. preparation method
Join in multi-dimensional movement mixing machine disposable above-mentioned each constituent materials, mix 10 minutes, again the material mixing is sent in the twin screw extruder with vacuum pumping function, at extruder screw rotating speed 90r/min, 60～220 DEG C of machine barrel and die temperatures, under vacuum exhaust vacuum gauge pressure-0.07MPa condition, plasticate extrude, cooling, oven dry and pelletizing obtain 40% depth of shade 1% thermal weight loss that can be applicable to direct formation of film at surface and be greater than the polyvinylidene difluoride (PVDF) (PVDF) of 320 DEG C high dense white master material for film.
3. film-forming properties checking
The polyvinylidene difluoride (PVDF) of above-mentioned preparation (PVDF) film is directly dropped into high dense white master material in the sandwich layer forcing machine of three-layer co-extruded PVDF cast film production line of 500mm fabric width and carry out the production of casting films masking, the three-layer co-extruded cast film characteristic of polyvinylidene difluoride (PVDF) of acquisition is as follows:
Membrane structure Film total thickness Core layer thickness Transmittance Film aberration Do not disperse color dot
Three layers 26μm 15μm 14％ Naked eyes have no Naked eyes have no
[comparative example]
Prepare double centner polyvinylidene difluoride (PVDF) (PVDF) film high density white master material
1. each composition weight is:
2. preparation method
Join in multi-dimensional movement mixing machine disposable above-mentioned each constituent materials, mix 10 minutes, again the material mixing is sent in the twin screw extruder with vacuum pumping function, at extruder screw rotating speed 90r/min, 60～220 DEG C of machine barrel and die temperatures, under vacuum exhaust vacuum gauge pressure-0.09MPa condition, plasticate extrude, cooling, oven dry and pelletizing obtain 40% depth of shade 1% thermal weight loss that can be applicable to direct formation of film at surface and be greater than the polyvinylidene difluoride (PVDF) (PVDF) of 320 DEG C high dense white master material for film.
3. film-forming properties checking
The polyvinylidene difluoride (PVDF) of above-mentioned preparation (PVDF) film is directly dropped into high dense white master material in the sandwich layer forcing machine of three-layer co-extruded PVDF cast film production line of 500mm fabric width and carry out the production of casting films masking, the three-layer co-extruded cast film characteristic of polyvinylidene difluoride (PVDF) of acquisition is as follows:
Membrane structure Film total thickness Core layer thickness Transmittance Film aberration Do not disperse color dot
Three-decker 25μm 13μm 17％ Naked eyes have no Visible once in a while

Claims (7)

1. a polyvinylidene difluoride film high density white master material, comprises that weight fraction is 30～80% white pigment, 5～35% dispersion agent, 0.1～5% pigment organic coating agent and the polyvinylidene fluoride resin of 5-52%.
2. polyvinylidene difluoride film high density white master material according to claim 1, it is characterized in that described white pigment is at least one in Rutile type Titanium Dioxide, anatase thpe white powder, zinc oxide, calcium carbonate, barium sulfate, zinc sulfide white, talcum powder, weight fraction is 30～60%.
3. polyvinylidene difluoride film high density white master material according to claim 1, it is characterized in that described dispersion agent is that polycondensate class, esters of acrylic acid, methyl acrylic ester, fatty acid ester, the molecular weight of polyprotonic acid and polyvalent alcohol is at least one in 1～1,000,000 ester analog thermoplastic high molecular polymer, polyethylene wax, weight fraction is 10～25%.
4. polyvinylidene difluoride film high density white master material according to claim 1, it is characterized in that the agent of described pigment organic coating is at least one in sodium laurylsulfonate, octadecanoic acid, stearin, titanic acid ester, silane, Aluminate, polyoxyethylene glycol, macrogol ester, weight fraction is 1～4%.
5. polyvinylidene difluoride film high density white master material according to claim 1, it is characterized in that described polyvinylidene fluoride resin is at least one in the polyvinylidene fluoride resin of the polyvinylidene fluoride polyamino alkenyl resin of molecular weight between 10～2,000,000 or modification by copolymerization, weight fraction is 10-45%.
6. the production method of polyvinylidene difluoride film use high density white master material described in claim 1, to comprise described white pigment, dispersion agent, the material of the agent of pigment organic coating and polyvinylidene fluoride resin adds in mixing tank according to described ratio or is directly fed and in twin screw extruder, carried out melt blending by feeding machine, twin screw extruder barrel zone temperature is 60～220 DEG C, screw speed is 50～200r/min, vacuum meter is with count-0.09～0MPa of gauge pressure, pass through screw rod shearing, mixing effect makes pigment in twin screw extruder, complete the molten organic coating of surperficial gas, and be dispersed in polyvinylidene fluoride resin with macromolecule dispersing agent, then carry out granulation, the dry polyvinylidene difluoride film high density white master material that makes.
7. the production method of high density white master material for polyvinylidene difluoride film according to claim 6, is characterized in that described twin screw extruder has vacuum pumping function.
CN201410254047.0A 2014-06-09 2014-06-09 High-concentration white master batch for polyvinylidene fluoride (PVDF) films and production method thereof Pending CN104059317A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104403240A (en) * 2014-11-13 2015-03-11 无锡中洁能源技术有限公司 High light-shading solar battery back membrane material and preparation method thereof
CN108410140A (en) * 2017-09-22 2018-08-17 浙江中迪纺织新材料科技有限公司 A kind of high molecular polymer white master material and preparation method thereof based on nano-aluminum hydroxide
CN109219506A (en) * 2016-05-31 2019-01-15 Ａｇｃ株式会社 The manufacturing method of fluororesin

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104403240A (en) * 2014-11-13 2015-03-11 无锡中洁能源技术有限公司 High light-shading solar battery back membrane material and preparation method thereof
CN109219506A (en) * 2016-05-31 2019-01-15 Ａｇｃ株式会社 The manufacturing method of fluororesin
CN108410140A (en) * 2017-09-22 2018-08-17 浙江中迪纺织新材料科技有限公司 A kind of high molecular polymer white master material and preparation method thereof based on nano-aluminum hydroxide

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