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WO2019158266A1 - Feuille de séparateur à propriétés mécaniques améliorées - Google Patents

Feuille de séparateur à propriétés mécaniques améliorées Download PDF

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Publication number
WO2019158266A1
WO2019158266A1 PCT/EP2019/000041 EP2019000041W WO2019158266A1 WO 2019158266 A1 WO2019158266 A1 WO 2019158266A1 EP 2019000041 W EP2019000041 W EP 2019000041W WO 2019158266 A1 WO2019158266 A1 WO 2019158266A1
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WIPO (PCT)
Prior art keywords
film
stretching
stretched
propylene
porous
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.)
Ceased
Application number
PCT/EP2019/000041
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German (de)
English (en)
Inventor
Bertram Schmitz
Thilo Mohr
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Treofan Germany GmbH and Co KG
Original Assignee
Treofan Germany GmbH and Co KG
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Publication of WO2019158266A1 publication Critical patent/WO2019158266A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/542—Shear strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a porous film and its use as a separator, and to a process for producing the film.
  • Modern devices require an energy source, such as batteries or rechargeable batteries, which enable a spatially independent use.
  • an energy source such as batteries or rechargeable batteries
  • more and more accumulators are used, which can be recharged with the help of chargers on the mains repeatedly.
  • nickel-cadmium (NiCd) batteries can achieve a lifetime of approximately 1000 charge cycles when used properly.
  • Batteries consist of two electrodes that dip into an electrolyte solution and a separator that separates the anode and cathode.
  • the different battery types differ by the electrode material used, the electrolyte and the separator used.
  • a battery separator has the task of spatially separating the cathode and anode in batteries, or negative and positive electrodes in accumulators.
  • the separator must be a barrier which electrically insulates the two electrodes from each other to avoid internal short circuits. At the same time, however, the separator must be permeable to ions so that the electrochemical reactions in the cell can proceed.
  • electrochemical double-layer capacitors are becoming increasingly important as a complementary source of energy, closing the gap between conventional batteries or rechargeable batteries and capacitors. By quickly absorbing and providing a high level of electrical power, they can either power an existing power source or supplement an existing generator or bypass a momentary power failure until an emergency power can be started with a time delay.
  • the design and manufacture of the DSK are comparable to those of lithium-ion batteries.
  • An electrochemical double-layer capacitor consists essentially of two electrodes immersed in an electrolyte solution and separated by the separator. This separator must be porous and absorb the electrolyte.
  • porous materials are selected, for example made of paper.
  • separators made of other materials such as plastic films, felts or fabrics made of plastic or glass fibers.
  • a plurality of electrode layers and separator layers are stacked alternately one over the other, for example as a planar stack or in the form of a coil.
  • the size of the gap between the two electrodes is determined by the thickness of the separator and possibly by any existing seals. So that the electrolyte / separator combination contributes as little as possible to the internal resistance, the separator should be thin and very porous, since the thickness is linear and the porosity approximately quadratic contribute to the electrical resistance.
  • the mechanical stresses during the winding or stacking process on the separator high mechanical demands in particular on the mechanical strength in the longitudinal direction, so that even in cell production, the separator thickness is limited down. Later in the cell thermal stability and in the given electrolyte sufficient chemical stability are required.
  • the thickness of the separator must be reduced or its porosity increased.
  • the increase in porosity leads to the reduction of mechanical stability.
  • At high porosity and at the same time small thickness of the separator then no longer has sufficient strength and there are problems in the processing of the separators, in the production of energy storage and ultimately in their use. Ultimately comes it reduces the lifetime and security problems of the cells.
  • rough, granular or particulate contaminated electrode surfaces easily pierce the separator, which is why a high puncture resistance is required.
  • separators made of biaxially oriented porous films have the advantage that they have a higher strength in the transverse direction than monoaxially oriented films, but the achieved strength in the longitudinal direction and the puncture strengths are no longer sufficient.
  • US Pat. No. 7,235,203 describes that a high orientation of the ⁇ -crystallites after the longitudinal stretching advantageously contributes to the formation of a high porosity. As a result, however, these porous films are not sufficiently stable in the transverse direction. For these reasons, biaxially oriented porous polypropylene films are produced today with a minimum thickness of 20 microns.
  • porous polyolefin films can be produced: filler method; Cold drawing, extraction process and ß-crystallite process. These methods are distinguished by the different mechanisms by which the pores are created.
  • filler porous films can be produced by the addition of very high amounts of filler porous films.
  • the pores are formed during stretching due to the incompatibility of the fillers with the polymer matrix.
  • the large amounts of filler of up to 40% by weight required to achieve high porosity compromise mechanical strength despite high draw considerably so that these products are not used as separators.
  • the pores are in principle produced by dissolving out a component from the polymer matrix by means of suitable solvents.
  • suitable solvents a variety of variants have developed, which differ in the nature of the additives and the appropriate solvents.
  • Both organic and inorganic additives can be extracted. This extraction can be done as the last step in the production of the film or combined with a subsequent drawing.
  • the process mainly produces polyethylene separators with good mechanical properties but low thermal resistance.
  • An older but successful process is based on stretching the polymer matrix at temperatures well below the melting point of the polymer (cold drawing).
  • the film is first extruded and then annealed to increase the crystalline content for a few hours.
  • the cold stretching is carried out in the longitudinal direction at very low temperatures in order to produce a plurality of defects in the form of the smallest microcracks.
  • This pre-stretched film with voids is then stretched in the same direction again at elevated temperatures with higher factors, enlarging the voids to pores forming a network-like structure.
  • These films combine high porosity and good mechanical strength in the direction of their drawing, generally the longitudinal direction. However, the mechanical strength in the transverse direction remains poor, whereby the puncture resistance is poor and results in a high splice tendency in the longitudinal direction. Overall, the process is costly.
  • Another known process for producing porous films is based on the admixture of ⁇ -nucleating agents to polypropylene.
  • the ß-nucleating agent forms the polypropylene during cooling of the melt so-called ß-crystallites in high concentrations.
  • the ⁇ phase is converted into the alpha modification of the polypropylene. Since these different crystal modifications differ in their density, many microscopic defects are also created here, which are torn to pores by stretching.
  • This process does not require any extraction step and is therefore also referred to in the art as a dry process (“dry process”) and thus delimited from the wet process with extraction (“wet process”).
  • the films produced by this process have good porosities and good mechanical strength in the longitudinal and transverse directions and a very good economy. These films are also referred to below as porous films.
  • this method can not produce high-strength films that can compete with the mechanical properties of the wet-process polyethylene separators.
  • the orientation can be increased in the longitudinal direction.
  • the orientation or stretching in the longitudinal direction to increase strength are therefore limited. Due to the inadequate mechanical strengths, when used as a separator, these ⁇ -porous films have a thickness of at least 20 ⁇ m in practice.
  • US Pat. No. 7,235,203 describes ⁇ -porous films with high porosities and Gurley values of less than 500 s / 100 ml, whose porosity is improved by a high orientation in the longitudinal direction.
  • the orientation in the longitudinal direction is increased by allowing a very high jump of 25 to 50% or more in the longitudinal direction.
  • a second method is described according to which needle-shaped crystals are used as ⁇ -nucleating agents. As a result of these needle-shaped crystals, the ⁇ -crystallites with a preferred orientation in the longitudinal direction are already formed on cooling of the melt to the prefilm. These longitudinally oriented crystals contribute to an increased orientation, so that after the longitudinal stretching a particularly high orientation in the longitudinal direction is present.
  • WO2011 134626A1 describes a process for producing a ⁇ -porous polypropylene film in which propylene polymer and ⁇ -nucleating agent is melted in an extruder, extruded through a flat die onto a take-off roll on which the melt film cools and solidifies to form ⁇ -crystallites. This film is then stretched longitudinally and then transversely, drawing in the transverse direction at a slow stretching speed of less than 40% / sec. By slow stretching in the transverse direction higher porosity can be achieved.
  • the type, size and distribution of the pores and the mechanical strengths of the films depend essentially on the basic process and differ considerably. In principle, however, the generation of a defect is always necessary in a first process step, which can then form a porous network structure of interconnected pores in a next stretching step.
  • vacuoles in the particle process relies on the generation of microcracks at the interface between the polymer and the particulate additive during longitudinal stretching. During the subsequent transverse stretching, these fine longitudinal cracks tear open to air-filled closed cavities or to a network of pores. It has been tried several times to produce these types of film by means of a simultaneous biaxial stretching. However, it was found that no comparable results could be achieved.
  • the porosity of the high filler content films was orders of magnitude lower than sequential stretching.
  • the object of the present invention was to provide a thin ß-porous film which has a high permeability and is improved in mechanical strength and thus can be used in reduced thicknesses as a separator in a variety of cell applications.
  • a biaxially oriented, single-layer or multi-layered film having at least one porous layer, this porous layer containing at least one propylene polymer and ⁇ -nucleating agent and the porosity of this porous layer by conversion of ⁇ -crystalline Polypropylene is produced in the stretching of the film, wherein the unstretched prefilm stretched in the longitudinal direction and then the longitudinally stretched film is stretched simultaneously in the longitudinal direction and in the transverse direction.
  • the problem underlying the invention is thus also achieved by a process for producing a biaxially oriented, single-layer or multilayer porous polypropylene film in which propylene polymer and ß-nucleating agent is melted in an extruder and extruded through a flat die onto a take-off roll on which the melt film under Formation of ⁇ -crystallites is cooled and solidified and the unstretched prefilm is stretched in the longitudinal direction and the longitudinally stretched film is then stretched simultaneously in the longitudinal direction and in the transverse direction.
  • the film according to the invention comprises at least one porous layer which is composed of propylene polymers, preferably propylene homopolymers and / or propylene block copolymers, and contains ⁇ -nucleating agents.
  • ⁇ -nucleating agents e.g., polyethylene glycol dimethacrylate copolymer
  • other polyolefins may additionally be included in minor amounts, provided they do not adversely affect porosity and other essential properties.
  • the porous layer additionally contains customary additives, for example stabilizers and / or neutralizing agents, in respective effective amounts.
  • Suitable propylene homopolymers contain from 98 to 100% by weight, preferably from 99 to 100% by weight of propylene units and have a melting point (DSC) of 150 ° C or higher, preferably 155 to 170 ° C, and generally a melt flow index of 0.5 to 10 g / 10 min, preferably 2 to 8 g / 10 min, at 230 ° C and a force of 2.16 kg (DIN 53735).
  • DSC melting point
  • isotactic propylene homopolymers having a high chain isotacticity of at least 96%, preferably 97-99% ( 13 C NMR, triad method) are used. These raw materials are called HIPP Polymers (high isotactic polypropylenes) or HCPP (high crystalline polypropylenes) are known in the art and are characterized by high stereoregularity of the polymer chains, higher crystallinity and higher melting point (compared to propylene polymers having a 13 C NMR isotacticity of 90 to ⁇ 96%, which can also be used).
  • Propylene block copolymers generally have a melting point above 140 to 170 ° C, preferably from 145 to 165 ° C, especially 150 to 160 ° C and generally a melt range of above 120 ° C, preferably in a range of 125-140th ° C begins.
  • the comonomer, preferably ethylene content is for example between 1 and 20 wt .-%, preferably 1 and 10 wt .-%.
  • the melt flow index of the propylene block copolymers is generally in a range of 1 to 20 g / 10 min, preferably 1 to 10 g / 10 min.
  • the porous layer may additionally contain other polyolefins, provided that they do not adversely affect the properties, in particular the porosity and the mechanical strengths.
  • Other polyolefins include, for example, random copolymers of ethylene and propylene having an ethylene content of 20% by weight or less, random copolymers of propylene with C 4 -C 8 olefins having an olefin content of 20% by weight or less, terpolymers of propylene, Ethylene and butylene having an ethylene content of 10% by weight or less and having a butylene content of 15% by weight or less, or polyethylenes such as LDPE, VLDPE, and LLDPE.
  • the porous layer is composed only of propylene homopolymer and / or Propylenblockcopolmyer and ß-nucleating agent, and optionally stabilizer and neutralizing agent.
  • ⁇ -nucleating agents for the porous layer.
  • Such ⁇ -nucleating agents as also their mode of action in a polypropylene matrix, are per se known in the art and will be described in detail below.
  • ⁇ -crystalline PP whose melting point is in the range from 155 to 170 ° C., preferably 158 to 162 ° C., is usually formed predominantly.
  • a small proportion of ⁇ -crystalline phase can be produced during cooling of the melt, which has a significantly lower melting point than the monoclinic a modification at 145-152 ° C., preferably 148-150 ° C.
  • additives are known which lead to an increased proportion of the ⁇ -modification during cooling of the polypropylene, for example ⁇ -quinacridones, dihydroquinacridines or calcium salts of phthalic acid.
  • highly active ⁇ -nucleating agents are preferably used which, on cooling a propylene homopolymer polymer melt, produce a ⁇ content of 40-95%, preferably of 50-85% (DSC).
  • the ⁇ content is determined from the DSC of the cooled propylene homopolymer melt.
  • preference is given to a two-component ⁇ -nucleation system composed of calcium carbonate and organic dicarboxylic acids, which is described in DE 3610644, to which reference is hereby expressly made.
  • Particularly advantageous are calcium salts of dicarboxylic acids, such as calcium pimelate or calcium suberate as described in DE 4420989, to which also expressly incorporated by reference.
  • the dicarboxamides described in EP-0557721, in particular N, N-dicyclohexyl-2,6-naphthalenedicarboxamides, are also suitable ⁇ -nucleating agents.
  • the cooling of the Melting film is preferably carried out at a temperature of 60 to 140 ° C, in particular 80 to 135 ° C, for example 95 to 130 or 1 10-125 ° C. Slow cooling also promotes the growth of ⁇ -crystallites, therefore, the withdrawal speed, ie the rate at which the melt film passes over the first chill roll, should be slow so that the residence times at the selected temperatures are sufficiently long.
  • the take-off speed is preferably less than 25 m / min, in particular 1 to 20 m / min.
  • the residence time of the melt film is generally 20 to 300 seconds; preferably 30 to 200s.
  • the porous layer generally contains 45 to ⁇ 100% by weight, preferably 50 to 95% by weight, of propylene homopolymer and / or propylene block copolymer and 0.001 to 5% by weight, preferably 50 to 10,000 ppm of at least one ⁇ -nucleating agent on the weight of the porous layer.
  • the proportion of propylene homopolymer or of the block copolymer is reduced accordingly.
  • the amount of the additional polymers in the layer will be 0 to ⁇ 10% by weight, preferably 0 to 5% by weight, in particular 0.5 to 2% by weight, if these are additionally present.
  • propylene homopolymer or propylene block copolymer portion is reduced when higher levels of up to 5 weight percent nucleating agent are employed.
  • the porous layer conventional stabilizers and neutralizing agents, and optionally further additives, in the usual small amounts of less than 2 wt .-%.
  • the porous layer is composed of a mixture of propylene homopolymer and propylene block copolymer.
  • the porous layer in these embodiments generally contains from 50 to 85% by weight, preferably from 60 to 75% by weight, of propylene homopolymers and from 15 to 50% by weight of propylene block copolymers, preferably from 25 to 40% by weight, and from 0.001 to 5 % By weight, preferably 50 to 10,000 ppm of at least one ⁇ -nucleating agent, based on the weight of the layer, and optionally the additives already mentioned, such as stabilizers and neutralizing agents.
  • polyolefins may be present in an amount of 0 to ⁇ 10 wt .-%, preferably 0 to 5 wt .-%, in particular 0.5 to 2 wt .-%, and the proportion of the propylene homopolymer or the Block copolymer is then reduced accordingly.
  • porous film according to the invention contain from 50 to 10,000 ppm, preferably from 50 to 5000 ppm, in particular from 50 to 2000 ppm of calcium pimelate or calcium suberate as ⁇ -nucleating agent in the porous layer.
  • the porous film may be one or more layers.
  • the thickness of the film is generally in a range of 3 to 100 ⁇ m, preferably 3 to 60 ⁇ m, in particular 3 to 50 ⁇ m.
  • film thicknesses of less than 10 .mu.m can be realized with the process according to the invention.
  • these porous thin films have a thickness of 3 to ⁇ 10 .mu.m, preferably a thickness of 3.5 to 8 .mu.m, in particular a thickness of 4 to 7 .mu.m.
  • the film comprises further porous layers which are constructed as described above, wherein the composition of the different porous layer need not necessarily be identical.
  • the thickness of the individual layers is generally 1 to 50 ⁇ m.
  • the density of the ⁇ -porous film is generally in a range of 0.1 to 0.6 g / cm 3 , preferably 0.2 to 0.5 g / cm 3 .
  • the film generally has a Gurley value of 10 to 500 s, preferably a Gurley value of 10 to 200 s.
  • the bubble point of the film is generally not more than 350 nm, preferably in the range from 20 to 300 nm, and the mean pore diameter is generally in the range from 40 to 100 nm, preferably in the range from 50 to 80 nm.
  • the present invention further relates to a process for producing the biaxially oriented ⁇ -porous film.
  • the porous film is produced by the known flat film extrusion or coextrusion process.
  • the procedure is such that propylene homopolymer and / or propylene block copolymer and ß-nucleating agent and optionally further polymers of the respective layer is mixed, melted in an extruder and, optionally together and simultaneously, extruded through a flat die on a take-off roll or coextruded / be on which solidifies the one- or multi-layer melt film to form the ß crystallites and cools.
  • the cooling temperatures and cooling times are chosen so that the highest possible proportion of ß-crystalline polypropylene in the unstretched prefilm arises.
  • this temperature of the take-off roll or the take-off rolls is 60 to 140 ° C, preferably 80 to 130 ° C.
  • the residence time at this temperature may vary and should be at least 20 to 300 seconds, preferably 30 to 100 seconds.
  • the prefilm thus obtained generally contains a proportion of ⁇ -crystallites of 40-95%, preferably 50-85%.
  • This prefilm with a high proportion of ⁇ -crystalline polypropylene is subsequently stretched such that upon stretching, the ⁇ -crystallites are converted into alpha-crystalline polypropylene and a network-like, porous structure is formed.
  • the longitudinal direction of the prefilm is stretched and then a simultaneous biaxial stretching in which the film is simultaneously stretched longitudinally (in the machine direction) and transversely (perpendicular to the machine direction) (LISIM or MESIM method).
  • the cooled prefilm is first passed over one or more heating rollers, which heat the film to the appropriate temperature. In general, this temperature is less than 140 ° C, preferably 70 to 120 ° C.
  • the longitudinal stretching is then generally carried out with the help of two according to the desired stretch ratio of different fast-running rollers.
  • the longitudinal draw ratio is in a range from 1, 5: 1 to 6: 1, preferably 2: 1 to 5: 1.
  • an orientation in the longitudinal direction of the width recess in the longitudinal sections are kept low, for example by setting a comparatively narrow stretch gap.
  • the length of the stretched gap for these embodiments is generally 3 to 100 mm, preferably 5 to 50 mm.
  • fixing elements such as spreaders contribute to a small latitude.
  • the jump should be less than 10%, preferably 0.5-8%, in particular 1-5% for these embodiments.
  • the film is first cooled again over appropriately tempered rolls or kept at the temperature.
  • the longitudinal stretching takes place in the so-called AufMapfeldern again heating to a suitable stretching temperature for the simultaneous stretching in the longitudinal and transverse directions.
  • This biaxial stretching is carried out simultaneously according to the invention.
  • a network-like porous structure is formed.
  • the desired network-like porous structure is formed, whereby at the same time the molecular chains of the polymer matrix are oriented.
  • simultaneous stretching processes include processes in which an unstretched prefilm is stretched simultaneously in the longitudinal and transverse direction by suitable devices.
  • suitable devices for carrying out the methods are known in the art, for example as LISIM or as MESIM (Mechanical Simultaneous Drawing) methods.
  • LISIM methods are described in detail in EP 1 112 167 and EP 0 785 858, to which reference is hereby expressly made.
  • An MESIM method is described in US 2006/01 15548, to which reference is also expressly made.
  • the ⁇ -porous film can also take place in a so-called diamond frame, in which a first separately prepared longitudinally stretched film is clamped, heated to the desired temperature and then by pulling the film in both directions simultaneously Longitudinal and transverse direction is stretched. (Articulated arms)
  • the simultaneous stretching takes place according to a continuous simultaneous stretching method.
  • the elongated film is transported in a stretching oven with a transport system, which works according to the LISIM ® method.
  • the film edges are detected by so-called clips, which be driven by a linear motor.
  • Individual clips for example, each Drite, are equipped with permanent magnets and also serve as a secondary part of a linear motor drive. Over almost the entire circulating transport path, the primary parts of the linear motor drive are arranged parallel to the guide rail.
  • the non-driven clips only serve to absorb film forces across the direction of travel and to reduce the sag between the stops.
  • the elongated film passes through a preheat zone in which the guide rails of the clips are substantially parallel.
  • the elongated film is heated from the inlet temperature to the stretching temperature by a suitable heating device, for example a convection heater or IR radiator.
  • a suitable heating device for example a convection heater or IR radiator.
  • the simultaneous stretching process begins by accelerating the mutually independent clip-on carriages in the direction of film travel (MD) and thus separating them, i. increase their distance from each other. In this way, the film is further stretched in length.
  • a transverse extension is superimposed on this process, specifically in that the guide rails diverge in the area of claw acceleration.
  • the biaxially stretched film is fixed in view of the desired mechanical film properties.
  • a heat setting at elevated temperature in which the film is optionally slightly relaxed in the longitudinal or transverse direction in the clamped state takes place.
  • Particularly advantageous may be the simultaneous relaxation in the longitudinal and transverse directions.
  • the speed of the clip-on wagon during or after the drawing process is reduced, which reduces their distance from each other and relaxation in the machine direction. Relaxation in the transverse direction is made possible by converging guide rails of the transport system.
  • the drawing speeds are varied during the stretching process. This process variant enables the LISIM process.
  • the clips can be accelerated more strongly when stretching the film, ie at the beginning of the simultaneous stretching process, resulting in a fast stretching speed at the beginning of the stretching process or additionally accelerated after stretching, which after a moderate stretching ansch manend to a faster stretching of the film in the frame leads.
  • the simultaneous stretching is carried out according to a principle equivalent to the LISIM method.
  • the longitudinally stretched film is here also transported in a stretching oven with a transport system of clips on guide rails.
  • a transport system of clips on guide rails At each edge of the film, there is a pair of rails on the opposite clips and clip-like elements are arranged and connected to each other via a scissors joint.
  • the scissors joint By the scissors joint, the distance between the clips can be varied. In which the scissors joint is pulled apart, the distance of the clips to each other increases. Conversely, the distance is reduced when moving the joint.
  • the two guide rails of the respective pair of rails are arranged converging, whereby the scissor joint is pulled apart and accelerate the clips in the direction of the film and increase their distances from each other.
  • the film is stretched further in length.
  • a simultaneous transverse extension takes place by the divergent arrangement of the rail pairs at each edge of the film, a simultaneous transverse extension.
  • the simultaneous stretching can take place on a laboratory stretching frame.
  • the stretched film is cut to the appropriate size and clamped in clips.
  • the clips are connected via scissor joints with rails that run in the transverse and longitudinal directions.
  • the clips hold the elongated film on its longitudinal and transverse sides.
  • the Frame is closed after clamping the film, then the film is heated in the frame via a heater fan a certain preheating and then stretched simultaneously in both directions.
  • the clips simultaneously pull apart the heated film over diverging rails. By speed and way of moving apart so different yield speeds and different stretch ratios can be realized.
  • the biaxially stretched film of the device can be removed directly or the film is still a certain time in the clamped state at a certain temperature. This can also be a relaxation.
  • the elongate film having a high content of ⁇ -crystalline polypropylene in the preheating zone or in the laboratory stretching frame is stretched to 90 to 160 ° C, preferably 110 to 150 ° C, at which the simultaneous stretching finally takes place.
  • the stretch ratios can be chosen flexibly, so that films with different Gurley values can be achieved depending on the application.
  • the longitudinal stretching factor in the subsequent simultaneous stretching can be increased to up to 10 (1000%), in particular up to 8 (80%), and thus lies well above the technically feasible longitudinal stretching factors in a sequential drawing.
  • the stretch factor in the longitudinal direction is 3 (300%) to 10 (1000%), in particular 4 (400%) to 8 (800%).
  • the stretch factor in the transverse direction is 5 (500%) to 7 (700%), especially 5 (500%) to 6 (600%).
  • exceptionally high surface stretch ratios can be realized.
  • Such area stretching ratios are not approachable in a sequential stretching. It is therefore surprising that overall a very high longitudinal stretching of ⁇ -porous films by means of the combined stretching according to the invention (first longitudinal stretching and then simultaneous stretching) is possible.
  • the sum of the longitudinal stretching factors is preferably in a range of 4 to 15, in particular in a range of 5 to 12.
  • the combined stretching thus enables surprisingly high area stretching ratios, which hitherto have not been achieved for biaxially stretched ⁇ -porous films and which preferably lie in the range from 20 to 100, in particular in the range from 30 to 80, in particular in the range from 40 to 70.
  • the simultaneous drawing is carried out with a moderate to slow stretching speed of> 0 to 40% / s, preferably in a range of 0.5 to 30% / s, in particular 1 to 15% / s.
  • the slow simultaneous stretching leads surprisingly to a higher porosity and higher permeability while maintaining good running safety of the film.
  • the stretching speed can in principle be varied over the speed of the method itself or over the length of the stretching frame. The faster (or slower) the production speed of the film (process speed) is, the higher (or the slower) is the stretch rate, each at a given stretch factor. Alternatively, the stretch may be increased by the same factor over a longer path, i. a longer stretching frame are performed to reduce the transverse stretching speed.
  • a surface of the film is corona, plasma or flame treated according to one of the known methods.
  • a heat-setting heat treatment
  • the film at the elevated temperature in the longitudinal or transverse direction controlled relax slightly in the clamped state.
  • Particularly advantageous may be the simultaneous relaxation in the longitudinal and transverse directions.
  • the clip-on wagons are decelerated, reducing their distance from each other.
  • the guide rails of the transport system are easily converged.
  • convergence means a slight collapse of the guide rails, so that the maximum width of the frame, which is given at the end of the stretching process, is greater than the width at the end of the heat-setting.
  • the degree of convergence of the stretching frame is expressed as the convergence calculated from the maximum width of the stretching frame B max and the final film width B foil according to the following formula:
  • the relaxation in the longitudinal direction or convergence in the transverse direction is within a range of 5 to 25%, in particular 8 to 20%.
  • the film is wound in the usual way with a winding device.
  • speeds of the drawing process is meant that speed, for example in m / min, with which the film runs during the final winding.
  • the process conditions in the process according to the invention for producing the porous films differ from the process conditions which are usually observed in the production of a biaxially oriented film.
  • both the cooling conditions when solidifying to the precursor film, and the temperatures and the factors involved in drawing are critical.
  • a high proportion of ß crystallites in the pre-film can be achieved.
  • the ⁇ -crystals of the polypropylene are converted into the alpha modification in such a way that, with the final simultaneous stretching, the porous network structure is formed.
  • the first stretch in the longitudinal direction initiates the conversion of ⁇ -crystallites into the alpha crystallites and generates a small number of defects in the form of microcracks.
  • these defects must initially be produced during the longitudinal stretching in sufficient numbers and in the correct form, whereby the process conditions during the longitudinal stretching can be varied only within a limited range.
  • the impurities are torn to pores, so that the characteristic network structure of these porous films is formed.
  • the novel combination process according to the invention initiates a small number of impurities during the first moderate longitudinal stretching and creates the network structure with the pores during the simultaneous stretching and allows high stretching forces to efficiently produce ⁇ -porous films with very good mechanical strengths and high porosities in small thicknesses .
  • the ⁇ -porous film according to the invention therefore has an outstanding combination of high porosity and permeability, mechanical strength, good running safety in the production process and low splice tendency in the longitudinal direction.
  • the film can be used advantageously in many applications in which very high permeabilities are required or have an advantageous effect.
  • a highly porous separator in batteries especially in lithium batteries with high performance requirements.
  • the melt flow index of the propylene polymers was measured according to DIN 53 735 at 2.16 kg load and 230 ° C.
  • the melting point in the context of the present invention is the maximum of the DSC curve.
  • a DSC curve is recorded with a heating and cooling rate of 10 K / 1 min in the range of 20 to 200 ° C.
  • the second heating curve after having been cooled at 10K / 1 min in the range of 200 to 20 ° C is evaluated. ß content of the prefilm
  • the determination of the ⁇ -content of the precursor film is likewise carried out by means of a DSC measurement which is carried out on the prefilmate film as follows:
  • the precursor film is first heated to 220 ° C. in the DSC at a heating rate of 10 K / min and melted and cooled again 1 heating curve, the degree of crystallinity K ß DSC is determined as the ratio of the enthalpies of fusion of the ⁇ -crystalline phase (H ß ) to the sum of the enthalpies of fusion of ß- and a-crystalline phase.
  • the density is determined according to DIN 53 479, method A.
  • Puncture resistance and puncture elongation is determined as described in ASTM F 1306. The measured puncture resistance divided by the film thickness then gives the relative puncture resistance in N / ⁇ m
  • Tear strengths, elongation at break and modulus of elasticity are determined using a standard tensile testing machine according to DIN EN ISO 527-1 / -3. For the measurements in the longitudinal direction, test strips in the machine direction and for the measurement in the transverse direction, test strips are cut out in the transverse direction.
  • the permeability of the films was measured with the Gurley Tester 41 10, according to ASTM D 726-58. It determines the time (in seconds) that 100 cm 3 of air will take to permeate through the 1 inch 2 (6,452 cm 2 ) film surface. The pressure difference across the film corresponds to the pressure of a water column of 12.4 cm in height. The time required then corresponds to the Gurley value.
  • the mixture additionally contained stabilizer and neutralizing agent in customary small amounts.
  • the melt was then extruded through a slot die and the hot melt film removed on a chill pick roll.
  • a take-off roll temperature of 120 ° C was selected, the take-off speed was 2 m / min.
  • the precursor had a ⁇ -crystallinity of 67%, which was determined by DSC.
  • Temperature take-off roll 120 ° C
  • the unstretched prefilm was first heated to approximately 110 ° C. by means of preheat rolls and then stretched in the longitudinal direction (MD machine direction) by a factor of 200%, then cooled to 60 ° C. by means of cooling rolls.
  • the cooled, elongated film was run at a speed of 4 m / min into the LISIM frame and heated to 140 ° C without stretching.
  • the heated longitudinally stretched film was then simultaneously stretched transversely and stretched 350% and wound at a speed of 14 m / min.
  • Example 2 The unstretched prefilm was heated to 110 ° C. as described in Example 1 and then stretched in the longitudinal direction by a factor of 250% and then cooled to 60 ° C. by means of cooling rolls before being then simultaneously drawn.
  • the cooled, longitudinally stretched film was run at a speed of 5 m / min in the LISIM frame and preheated without stretching to 140 ° C and then simultaneously 550% transversely stretched and 350% elongated and wound at a speed of 17.5 m / min
  • the unstretched prefilm was heated to 110 ° C. as described in Example 1 and then stretched in the longitudinal direction by a factor of 400% and then cooled to 60 ° C. by means of cooling rolls before being then drawn simultaneously.
  • the cooled, longitudinally stretched film was at a speed of 8 driven in the LISIM frame and preheated without stretching to 140 ° C and then simultaneously 550% transversely stretched and 350% longitudinally stretched and wound up at a speed of 24m / min.
  • the following process conditions were set:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Cell Separators (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille monocouche ou multicouche à orientation biaxiale pourvue d'au moins une couche poreuse en polymère propylène et en agent de β-nucléation. La porosité est produite par conversion de polypropylène β-cristallin lorsque la feuille est étirée, la feuille préformée non étirée étant d'abord tendue dans la direction longitudinale et ensuite la feuille tendue longitudinalement étant étirée simultanément dans la direction longitudinale et dans la direction transversale.
PCT/EP2019/000041 2018-02-16 2019-02-14 Feuille de séparateur à propriétés mécaniques améliorées Ceased WO2019158266A1 (fr)

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DE102018001242.6 2018-02-16

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116277827A (zh) * 2023-04-10 2023-06-23 河北海伟电子新材料科技股份有限公司 聚丙烯薄膜、金属化薄膜、电容器、制备方法及用途
CN116638742A (zh) * 2023-04-28 2023-08-25 厦门法拉电子股份有限公司 一种聚丙烯膜的制备方法及聚丙烯膜、金属化聚丙烯膜、电容器

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DE3610644A1 (de) 1985-04-01 1986-10-02 Shanghai Institute of Organic Chemistry Academia Sinica, Shanghai Ss-kristallines isotaktisches polypropylen, verfahren zu seiner herstellung und daraus hergestellte koerper
EP0557721A2 (fr) 1992-01-24 1993-09-01 New Japan Chemical Co.,Ltd. Composition de polypropylène crystallin et composés à fonctions amide
DE4420989A1 (de) 1994-06-16 1995-12-21 Danubia Petrochem Deutschland Verfahren zur Erhöhung des Anteils der ß-Modifikation in Polypropylen
EP0785858A1 (fr) 1994-10-13 1997-07-30 Brückner Maschinenbau GmbH Dispositif de fabrication de bandes de feuilles etirees en longueur et/ou en largeur, notamment etirees en meme temps le long de deux axes
EP1112167A1 (fr) 1998-09-08 2001-07-04 Brückner Maschinenbau GmbH Procede de production d'un film a orientation biaxiale constitue d'un polymere thermoplastique orientable mousse
WO2003033574A1 (fr) 2001-10-15 2003-04-24 Ucb, S.A. Film polymere etire et vide
US20060115548A1 (en) 2003-01-15 2006-06-01 Innocente Marchante Moreno Simultaneous longitudinal and transverse film drawing device
US7235203B2 (en) 2001-02-21 2007-06-26 New Japan Chemical Co., Ltd. Successively biaxial-oriented porous polypropylene film and process for production thereof
WO2011134626A1 (fr) 2010-04-26 2011-11-03 Treofan Germany Gmbh & Co. Kg Feuille séparatrice hautement poreuse
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US20140127492A1 (en) * 2012-11-06 2014-05-08 Celgard, Llc Copolymer membranes, fibers, products and methods
US20150267016A1 (en) * 2014-03-21 2015-09-24 Celgard, Llc Seam tape and methods of manufacture and use thereof

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EP0557721A2 (fr) 1992-01-24 1993-09-01 New Japan Chemical Co.,Ltd. Composition de polypropylène crystallin et composés à fonctions amide
DE4420989A1 (de) 1994-06-16 1995-12-21 Danubia Petrochem Deutschland Verfahren zur Erhöhung des Anteils der ß-Modifikation in Polypropylen
EP0785858A1 (fr) 1994-10-13 1997-07-30 Brückner Maschinenbau GmbH Dispositif de fabrication de bandes de feuilles etirees en longueur et/ou en largeur, notamment etirees en meme temps le long de deux axes
EP1112167A1 (fr) 1998-09-08 2001-07-04 Brückner Maschinenbau GmbH Procede de production d'un film a orientation biaxiale constitue d'un polymere thermoplastique orientable mousse
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WO2003033574A1 (fr) 2001-10-15 2003-04-24 Ucb, S.A. Film polymere etire et vide
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US20120171548A1 (en) * 2009-06-20 2012-07-05 Treofan Germany Gmbh & Co. Kg Microporous foil for batteries having shutdown function
WO2011134626A1 (fr) 2010-04-26 2011-11-03 Treofan Germany Gmbh & Co. Kg Feuille séparatrice hautement poreuse
WO2013080867A1 (fr) * 2011-11-28 2013-06-06 東レ株式会社 Film poreux, séparateur pour dispositif de stockage électrique et dispositif de stockage électrique
US20140127492A1 (en) * 2012-11-06 2014-05-08 Celgard, Llc Copolymer membranes, fibers, products and methods
US20150267016A1 (en) * 2014-03-21 2015-09-24 Celgard, Llc Seam tape and methods of manufacture and use thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116277827A (zh) * 2023-04-10 2023-06-23 河北海伟电子新材料科技股份有限公司 聚丙烯薄膜、金属化薄膜、电容器、制备方法及用途
CN116638742A (zh) * 2023-04-28 2023-08-25 厦门法拉电子股份有限公司 一种聚丙烯膜的制备方法及聚丙烯膜、金属化聚丙烯膜、电容器

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