WO2019004303A1 - 高濃度粒子含有フィルム及びその製造方法 - Google Patents
高濃度粒子含有フィルム及びその製造方法 Download PDFInfo
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- WO2019004303A1 WO2019004303A1 PCT/JP2018/024437 JP2018024437W WO2019004303A1 WO 2019004303 A1 WO2019004303 A1 WO 2019004303A1 JP 2018024437 W JP2018024437 W JP 2018024437W WO 2019004303 A1 WO2019004303 A1 WO 2019004303A1
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- diamine
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Definitions
- the present invention relates to a high concentration particle-containing film containing high concentration of particles, and more particularly to a high concentration particle-containing film suitable as a material of an electronic member.
- Films made of high molecular polymers are widely used as materials for various electronic members such as batteries, capacitors, electric double layer capacitors and the like.
- the required properties include conductivity in a state where an electrolyte is held, high inter-electrode shielding properties, low internal resistance, and the like.
- it is required to suppress heat generation and ignition at the time of short circuit.
- a measure is taken such as coating on one side.
- Patent Document 1 a hydrophilic resin containing ceramic particles is coated on one side of a polyethylene porous film as a separator material which is a partition material between electrodes, and a para-aromatic polyamide (para-aramid) is coated on the opposite side.
- a para-aromatic polyamide para-aramid
- the para-based aromatic polyamide needs to have a low molecular weight, which is obtained in this manner.
- the dispersed solution has low stability, and the polymer coagulates and precipitates quickly, so that the control of the stability of the coating film (for example, the stability regarding the film thickness, the uniformity of the components, the strength of the film, etc.) and the coating process Another problem occurred, such as being difficult.
- the stability of the coating film for example, the stability regarding the film thickness, the uniformity of the components, the strength of the film, etc.
- the method of coating and using the base material which concerns on a high heat resistant functional layer is employ
- the high heat resistant layer for example, an inorganic fine particle layer is used.
- a polymer is used as a binder between particles, and a thin film of a polymer containing inorganic fine particles is coated on a substrate.
- aromatic polyamides hereinafter sometimes referred to as "aramids”
- Araramids aromatic polyamides
- Patent Document 2 Examples of common aromatic polyamides include poly-p-phenylene terephthalamide (Patent Document 2).
- Patent Document 2 poly-p-phenylene terephthalamide
- the molecules tend to form domains with each other in the solution due to its liquid crystallinity, and it changes into a non-uniform aspect that is difficult to redisperse, so the solution storage stability It was scarce.
- JP 2012-54230 A Japanese Patent Application Laid-Open No. 10-279795
- the present invention is to solve the problems of the prior art and to provide a high concentration particle-containing film excellent in flexibility while containing a large amount of particles, and a method for producing the same.
- ⁇ Aspect 1 Para-based aromatic polyamide co-polymerized with para-phenylene diamine, copolymer diamine, and para-terephthalic acid dichloride, and particles
- the copolymerized diamine is in a range of 25 to 75% by weight in a weight ratio to all diamine components, and the particles are contained in 55% by volume or more
- the copolymerization diamine is 3,3 'oxydiphenylene diamine, 3,4' oxy diphenylene diamine, or 4,4 'oxy diphenylene diamine.
- High concentration particle-containing film ⁇ Aspect 2> The film according to aspect 1, wherein the content of the particles is 55% by volume to 98% by volume.
- a laminate comprising the film according to any one of aspects 1 to 6 and a substrate.
- ⁇ Aspect 10> It is a processing solution containing para-based copolymerized aromatic polyamide, particles, and an organic solvent, wherein the ratio of said particle based on the solid content of said para-based copolymerized aromatic polyamide and said particles in said treated solution is 66% by weight.
- Aspect 11 It is a processing solution containing para-based copolymerized aromatic polyamide, particles, and an organic solvent, wherein the ratio of said particle based on the solid content of said para-based copolymerized aromatic polyamide and said particles in said treated solution is 66% by weight
- the manufacturing method of the laminated body as described in aspect 7 or 8 which applies the processing solution which is the above, and is integrated on a base material.
- ⁇ Aspect 12> The production method according to aspect 10 or 11, wherein the ratio of the particles to the solid content of the treatment liquid is 75 to 99% by weight.
- a separator for a lithium ion secondary battery comprising the laminate according to aspect 7 or 8.
- Aspect 14 Use of the film according to any one of Aspects 1 to 6 or the laminate according to Aspect 7 or 8 as a separator of a lithium ion secondary battery.
- a high concentration particle-containing film excellent in flexibility while containing a large amount of particles and a method for producing the same are provided.
- the high concentration particle-containing film of the present invention is one in which the polymer component is mainly composed of a nitrogen-containing aromatic polymer and contains 55% by volume or more of particles.
- the high concentration particle-containing film of the present invention is a film in which the film form is mainly held by the polymer component, but the main component of the polymer component, preferably 70% by volume or more, particularly 90% by volume or more It is preferred to be composed of an aromatic polymer.
- examples of the nitrogen-containing aromatic polymer used as the polymer component of the present invention include aromatic polyamide (hereinafter sometimes referred to as “aramid”), aromatic polyimide, aromatic polyamideimide and the like, among which aromatic It is preferable that it is resin which consists of family polyamide, and it is especially preferable that it is para-type aromatic polyamide (Hereinafter, it may be mentioned “para aramid”) which is excellent in physical characteristics, heat resistance, and a low heat-shrinkage characteristic.
- aromatic polyamide hereinafter sometimes referred to as “aramid”
- aromatic polyimide aromatic polyimide
- aromatic polyamideimide aromatic polyamideimide
- para-type aromatic polyamide hereinafter, it may be mentioned “para aramid” which is excellent in physical characteristics, heat resistance, and a low heat-shrinkage characteristic.
- the nitrogen-containing aromatic polymer preferably contains an oxydiphenylene component, which makes it possible to improve the flexibility of the film.
- this nitrogen-containing aromatic polymer is a copolymer aromatic polyamide.
- it is a para-copolymerized aromatic polyamide, and 3,3 'oxydiphenylene diamine, 3,4' oxydiphenylene diamine or 4,4 'in which the copolymerization diamine component contains an oxydiphenylene component. It is preferable that it is oxydiphenylene diamine.
- polyparaphenylene terephthalamide obtained by polymerizing paraphenylene diamine and paraterephthalic acid dichloride is widely known as general para-aramid (for example, "Twaron (trademark)” manufactured by Teijin Limited).
- general para-aramid for example, "Twaron (trademark)” manufactured by Teijin Limited.
- this poly (p-phenylene terephthalamide) exhibits liquid crystallinity, and it is easy for molecules to form domains mutually, and once it is possible to form domains again, it is difficult to re-disperse in homogeneous solution. Was scarce.
- it since it contains a large amount of particles, it is preferable to increase the solubility of the polymer component to be used in an organic solvent or to suppress liquid crystallinity and the like, and it is preferable to contain a copolymerized diamine component.
- a polymer used especially for this invention as a copolymerization diamine component of this nitrogen-containing aromatic polymer, it is preferable that it is a component which introduce
- the para-copolymerized aromatic polyamide is (1) para-phenylene from the viewpoint of solubility in an organic solvent and stability of the solution. It is preferable that it is what is comprised by diamine, (2) copolymerization diamine, and (3) paraterephthalic acid dichloride.
- this copolymerized diamine 3,3 'oxydiphenylene diamine, 3,4' oxy diphenylene diamine or 4,4 'oxy diphenylene diamine can be mentioned.
- the solubility in the polar organic solvent can be enhanced, and the handling property, and hence the film physical properties are improved.
- this copolymerization diamine component 3,3 'oxydiphenylene diamine, 3,4' oxy diphenylene diamine or 4,4 'oxy diphenylene diamine is suitable.
- the proportion of the copolymerized diamine component in the amine component is preferably 25 to 75% by weight.
- the ratio of a suitable copolymerized diamine component is preferably in the range of 40 to 60% by weight in the amine component.
- the intrinsic viscosity (IV) measured at 30 ° C. for a solution having a polymer concentration of 0.5 g / dl in concentrated sulfuric acid having a concentration of 98% is 1.5 to 2.6 or 3.3 to 5 It is preferable to be in the range of .0.
- the para-based copolymerized aromatic polyamide can have a number average molecular weight (Mn) of 10000 or more, 20000 or more, 25000 or more, or 30000 or more, and 150,000 or less, 100000 or less, 80000 or less, or 75000 The following can be defined.
- Mn number average molecular weight
- the number average molecular weight in the present invention can be measured by gel permeation chromatography (GPC).
- the number average molecular weight of the para-based copolymerized aromatic polyamide is 10000 or more, the entanglement points of polymer chains formed at the time of film formation are increased, so that the film formability and mechanical properties of the film can be further improved. it can.
- the heat shrinkage rate of the film obtained from the polyamide can be further reduced.
- the heat shrinkage rate of such a laminate, in particular 150 The thermal contraction rate in ° C can also be reduced.
- the heat shrinkage reduction effect is considered to be due to the fact that particles contained in a high concentration in the film are relatively uniformly dispersed by using a relatively low molecular weight polymer.
- Para-based copolymerized aromatic polyamides have a weight-average molecular weight (Mw) / number-average molecular weight (Mn) (hereinafter referred to as “molecular weight distribution”) from the viewpoints of heat shrinkage characteristics, film forming properties to a substrate, film strength, etc. ) May be defined as 10.0 or less, 8.0 or less, or 5.0 or less, and this value may be 1.0 or more, 2.0 or more, or 3.0 or more. It may be.
- para-based copolymerized aromatic polyamides it is considered that the constituent diamine components carry out a plurality of block copolymerizations. Then, for example, when para-based copolymerized aromatic polyamide is fiberized and stretched at a high temperature, clear reflection can be detected by X-ray analysis. However, when this polymer is heat-treated at 400 ° C., the X There is a phenomenon that the reflection of line analysis becomes unclear.
- polyparaphenylene terephthalamide structure parts are brought close to each other by interaction to form a domain, and a copolymerized diamine component 3,3 'oxydiphenylene diamine, 3,4' oxydiphenylene diamine or 4,4 ' It is considered that the portion having oxydiphenylenediamine as a component is present as a soft segment.
- the presence of this soft segment is considered to be a major factor that enables the film flexibility to be maintained even if a large amount of particles are contained as the polymer component freely diffuses in the solvent to form a network structure. .
- 3,4'-oxydiphenylenediamine having a particularly well-defined molecular bending structure as a copolymerized diamine component in the molecular chain of the polymer.
- the molecules constituting the polymer are not oriented, and it is preferable that the film is a cast film or the like not subjected to stretching or the like.
- non-oriented films also have the advantage of low thermal shrinkage.
- the polymer component is mainly a nitrogen-containing aromatic polymer, and further, by including the copolymerized diamine component as described above in the polymer component, the particles are embrittled even when contained at a high concentration. Therefore, it became possible to make the film flexible.
- the para-based copolymerized aromatic polyamide having at least one of the above-described number average molecular weight and molecular weight distribution may be prepared by control of polymerization when obtaining such an aromatic polyamide, or a para-based copolymerized aromatic having a large molecular weight It may be prepared by reducing the molecular weight of the group polyamide.
- the method by molecular weight reduction treatment is preferred.
- the low molecular weight treatment is performed, for example, by breaking the molecular chain of the para-copolymerized aromatic polyamide by immersion treatment in an alkali or immersion treatment in an acid.
- the immersion treatment to an acid the decomposition reaction of the aromatic polyamide hardly occurs, and it is necessary to set a severe reaction temperature and reaction time.
- the method by the immersion treatment to the alkali which can reduce molecular weight under relatively mild conditions is preferable. By using this method, the molecular weight can be effectively reduced without impairing the uniform distribution of molecular weight.
- para-based copolymerized aromatic polyamides of various number average molecular weights can be obtained from para-based copolymerized aromatic polyamides of common high molecular weight by appropriately setting the immersion conditions. it can.
- the temperature of immersion treatment can be, for example, 80 to 140 ° C.
- the concentration of alkali is, for example, 1 to 10 weight when using NaOH as alkali %
- immersion time may be, for example, 30 minutes to 2 hours.
- the temperature of the immersion treatment is higher than the above conditions, the alkali concentration is high, or the time of the immersion treatment is long, the polymer decomposition by the alkali proceeds excessively and the polymer after the treatment is deteriorated, and the mechanical properties are deteriorated. In addition to being prone to occur, it is not desirable because the heating step or the neutralization step after the treatment requires a large process cost.
- the para-based copolymerized aromatic polyamide can be effectively and uniformly reduced in molecular weight It is difficult to obtain a para-based copolymerized aromatic polyamide having at least one of the above-mentioned number average molecular weight and molecular weight distribution.
- the particles are not particularly limited as long as they do not dissolve when mixed with the polymer and maintain the particle shape. Furthermore, organic particles such as inorganic particles and crystalline polymers that are difficult to dissolve are preferable. Among them, inorganic particles are preferable from the viewpoint of obtaining good heat resistance.
- the particles can be used alone or in combination.
- the high concentration particle-containing film of the present invention contains 55% by volume or more of particles. Furthermore, the content of the particles is preferably 65% by volume or more, and particularly preferably 75% by volume or more. The upper limit thereof is preferably 99% by volume or less, 98% by volume or less, and more preferably 95% by volume or less.
- the film can be made porous by containing particles in this range. Since the film is porous, for example, in the use of the separator, the heat resistance and the low heat shrinkage of the separator can be improved without inhibiting the movement of the necessary ions.
- the volume content ratio (volume%) is a ratio converted to a volume according to the respective material density from the weight of the polymer and the weight of the particles present in the film. Therefore, the void etc. in the film become the abundance ratio in the solid volume excluding.
- the weight ratio is preferably 66% by weight or more, more preferably 75 to 99% by weight, and particularly preferably 80 to 95% by weight.
- the content of the particles is too small, the space between the particles increases and the proportion of the polymer increases, so that the heat resistance and the like decrease.
- the content of the particles is too large, there is a concern that formation of the surface state of the film may be difficult or the physical properties of the film may be deteriorated.
- the present invention it is possible to generate minute voids in the film by further increasing the ratio of particles to extremely reduce the ratio of the polymer component or stretching at a low temperature after film formation.
- the content of the polymer is suppressed to the volume ratio or less of the total void volume of the particles at the closest packing, the film is remarkably voided.
- the packing ratio of the particles is only 0.74 in the hexagonal close-packed or face-centered cubic lattice structure (in addition, 0 in the body-centered cubic lattice structure). 68, 0.52 for simple cubic lattice structures, 0.38 for diamond structures). Therefore, especially when the content of particles is 75% by volume or more, such as containing particles exceeding the closest packing ratio, the polymer (resin) can not be completely filled between the particles, and a large number of fine particles are contained. Form a porous structure film.
- the voids are mainly generated in the gaps between the particles and the polymer.
- inorganic particles and organic particles such as poorly soluble polymers are preferable.
- the inorganic particle is preferably a metal particle, an oxide compound, a semiconductor element, a semiconductor compound or the like, and as the hardly soluble polymer, it is possible to use various fillers such as a crystalline polymer or cellulose nanofiber which does not dissolve in a solvent. Can.
- particles of 1 mm or less can be used as the particles used in the present invention, fine particles are preferable.
- the average particle diameter of the fine particles is preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less. In particular, the range of 0.01 ⁇ m or more and 2 ⁇ m or less is more preferable.
- the shape of the particles may be a polygonal shape as it is crushed, a spherical shape, a rugby ball shape, a gourd shape with a constriction, a needle shape having a large aspect ratio, a plate shape or the like.
- the shape of the fine particles is other than spherical, the length in the direction showing the maximum length of the particles is taken as the particle diameter.
- two or more different types of particles may be simultaneously contained. By using a plurality of particles having different particle sizes, it is possible to obtain a more highly loaded polymer film.
- semiconductor materials such as silicon, silicon carbide (SiC) and germanium, silicon nitride (silicon nitride), aluminum nitride (aluminum nitride), boron nitride (boron nitride)
- Nitride compounds such as polyimide, carbon black, diamond, graphene, fullerene, carbon nanotubes, carbon nanofibers, carbon materials such as graphite, and the like. It is also preferable to use mineral fine particles such as kaolin, talc, clay, hydrotalcite, diatomaceous earth and the like.
- inorganic particles calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, Alumina, mica, zeolite, glass and the like can also be mentioned.
- Inorganic particles are particularly excellent from the viewpoint of heat resistance and chemical stability, and among them, silica, kaolin, carbon black and the like are preferable. Each of these inorganic particles may be used alone, or two or more types of inorganic particles may be mixed and used.
- Such a high concentration particle-containing film of the present invention preferably has a thickness of 300 ⁇ m or less. Furthermore, depending on the application, it is preferably in the range of 1 to 200 ⁇ m. For example, in the case of using as a separator heat-resistant coating of LiB, LiC or the like, the thickness is preferably in the range of 1 to 20 ⁇ m, and more preferably in the range of 1 to 4 ⁇ m. Since the high concentration particle-containing film of the present invention has high physical properties, it has become possible to reduce its internal resistance by making it thinner than before. The heat resistance is also high, and it is possible to sufficiently cope with the shrinkage stress of the porous PE film and the like due to the thermal runaway when the separator is damaged.
- the thickness is preferably in the range of 10 to 50 ⁇ m, and when used as a heat-resistant flame-resistant layer, a thick film of 100 ⁇ m or more is also preferable. In an extreme case, it is a thick film of about 1 mm or less when used as a partition, or a film of about 2 to 8 mm thick when used as a heat conduction (heat sink), and it is smooth as a whole. It is also preferable that it is a fin shape of convex shape (mountain shape).
- Thermal shrinkage of the high concentration particle-containing film of the present invention or a laminate comprising the film is obtained by cutting out the obtained sample at a predetermined size and placing it in a dryer set at a predetermined temperature, from dimensional change before and after heat drying. It can be asked.
- the heat shrinkage ratio of the high concentration particle-containing film of the present invention can be defined, for example, as 10% or less, 5% or less, or 2% or less for a film with a thickness of 20 ⁇ m before heat treatment at 150 ° C.
- the heat shrinkage ratio of a laminate including a 4 ⁇ m thick film and a 10 ⁇ m thick polyethylene porous substrate (F10CF1 manufactured by Toray Industries, Inc.) before heat treatment at 150 ° C. is 50% or less, 40% or less
- a thermal contraction rate intends at least one of two directions of a parallel direction (MD) and a perpendicular direction (TD) with respect to the delivery direction of the substrate.
- Gurley value, ⁇ Gurley value per unit thickness Gurley measurement was performed according to JIS P8117 (Gurley air permeability measurement method).
- a sample in the measurement for example, a sample of a laminate made of a porous substrate to which a high concentration particle-containing film is applied can be used.
- a value obtained by subtracting the Gurley value of the porous substrate from the measurement value of the sample can be taken as the ⁇ Gurley value.
- the ⁇ Gurley value per unit thickness can be determined as the ⁇ Gurley value per unit thickness divided by the film thickness.
- the ⁇ Gurley value for the high concentration particle-containing film of the present invention can be specified as 65 seconds / 100 cc or less, 60 seconds / 100 cc or less, or 55 seconds / 100 cc or less.
- the ⁇ Gurley value per unit thickness for the high concentration particle-containing film of the present invention 30 seconds / 100 cc / ⁇ m or less, 25 seconds / 100 cc / ⁇ m or less, or 20 seconds / 100 cc / ⁇ m or less Can.
- the treatment solution is a solution containing particles and a polymer dissolved in an organic solvent
- the polymer in the treatment solution is mainly a nitrogen-containing aromatic polymer
- the ratio of particles to the solid content in the treatment solution is It is 66% by weight or more
- the processing solution is applied onto a substrate to form a film.
- the content of the particles in the treatment solution needs to be 66% by weight or more of the total amount of the polymer and the particles after drying, but it is further 75 to 99% by weight, in particular 80 to 95% by weight. A range is preferred.
- the high concentration particle-containing film obtained by such a production method preferably contains 55% by volume or more of particles in the film after drying. Furthermore, the content of the particles is preferably 65% by volume or more, and particularly preferably 75% by volume or more. The upper limit thereof is preferably 99% by volume or less, 98% by volume or less, and more preferably 95% by volume or less.
- the volume content ratio (volume%) is the ratio of the volume of particles to the total of the volume of polymer and the volume of particles present in the film, as described above. That is, the void etc. in a film become an abundance ratio in the solid volume excepted.
- a smooth glass plate or a synthetic resin film can be used as a substrate used to form a film in the production method of the present invention, and a polyester film or the like having an inactive surface is preferably used as the synthetic resin film.
- a treatment liquid containing a polymer on a substrate is applied using a so-called cast method in which coating is performed with a coating bar provided with a clearance or a treatment liquid having fluidity is poured. It is preferable to deposit and dry at a low temperature of 100 ° C. or less to form a film.
- the production method of the present invention for example, after a nitrogen-containing aromatic polymer is used as the main component of the polymer component and the polymer component is dissolved in an organic solvent, particles are added and defoamed, etc. And film forming methods are preferred. At this time, it is preferable that the particles do not dissolve in the organic solvent that dissolves the polymer component, and maintain the particle shape.
- the main component of the polymer component is a nitrogen-containing aromatic polymer, particularly a polymer such as an aromatic polyamide which is preferably used in the high concentration particle-containing film of the present invention.
- the nitrogen-containing aromatic polymer is preferably a para-copolymerized aromatic polyamide, and further, as a copolymerized diamine component, an oxydiphenylene component, 3,3 'oxydiphenylene diamine, 3,4' oxy It is preferable to contain diphenylene diamine or 4,4 'oxydiphenylene diamine.
- organic solvent which dissolves the polymer for example, organic polar amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, tetrahydrofuran, dioxane
- organic polar amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, tetrahydrofuran, dioxane
- water-soluble ether compounds such as methanol, ethanol and ethylene glycol
- water-soluble ketone compounds such as acetone and methyl ethyl ketone
- water-soluble nitrile compounds such as acetonitrile and propionitrile.
- NMP N-methyl-2-pyrrolidone
- the polymer concentration in the organic solvent containing this polymer component is preferably a dilute solution, and the polymer solid concentration is 10% by weight or less, in particular 0.1 to 4 weight. It is preferably in the range of%.
- the voids between the particles and the polymer are generated by performing drawing or length treatment at a low temperature, for example, 100 ° C. or less, more preferably 80 ° C. or less. Is also preferred.
- a high concentration particle-containing film obtained by film formation on a substrate such as a glass plate can be peeled from the substrate to prepare a self-supporting film, while the above-mentioned treatment solution can be used. It can also be applied onto a substrate to prepare a laminate in which the high concentration particle-containing film and the substrate are integrated.
- the film in the case of the laminated configuration, the film may be referred to as a layer or a thin film.
- the high concentration particle-containing thin film of the present invention comprises a substrate and a coating solution containing particles and a para-copolymerized aromatic polyamide having at least one of the above-mentioned number average molecular weight and molecular weight distribution dissolved in an organic solvent. It can also be obtained by applying to and drying.
- the polymer concentration in the coating solution can be 1.5 wt% or more, 2.0 wt% or more, or 2.5 wt% or more, and 7 wt% or less, 6 wt% % Or less, 5% by weight or less, or 4% by weight.
- the polymer concentration in consideration of an increase in environmental load and production cost accompanying an increase in the amount of solvent used, it is preferable to set the polymer concentration to a higher concentration, in particular, 2.5% by weight or more or 3.0% by weight or more .
- PPTA poly (p-phenylene terephthalamide)
- the concentration of the polymer in the coating solution is high, crystallization and gelation tend to occur easily.
- para-based copolymerized aromatic polyamides In such a case, at least in the above concentration range, it has the advantage of not exhibiting such a tendency.
- the viscosity of the coating solution can be specified as 400 mPa ⁇ S or more, 450 mPa ⁇ S or more, or 500 mPa ⁇ S or more at normal temperature from the viewpoint of coating property to the substrate, etc., and 5000 mPa ⁇ s. S or less, 4,000 mPa ⁇ s or less, or 3,000 mPa ⁇ s or less can be defined.
- normal temperature in the present disclosure intends a temperature range of 15 to 25 ° C.
- a base material that can be used in such a laminate for example, a non-woven fabric or a porous base material, particularly, a porous film can be used, and as these materials, polyolefin resins such as polyethylene, polyethylene terephthalate (PET And polyester resins such as polyethylene naphthalate (PEN) can be used.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- Example 1 In Example 1, the porosity, mechanical strength and flexibility of the high concentration particle-containing film were evaluated.
- Para-based copolymerized aromatic polyamide was used as the nitrogen-containing aromatic polymer. That is, it is composed of (1) paraphenylene diamine, (2) copolymer diamine, (3) paraterephthalic acid dichloride, and the copolymer diamine component is 3,4 'oxydiphenylene diamine, which is a copolymer diamine component A "Technola (trademark)" powder manufactured by Teijin Ltd., in which the proportion in the amine component is 50% by weight, was prepared. When this was used as a film, the density was 1.39 g / cm 3 . In addition, the intrinsic viscosity (IV) measured at 30 ° C. for a solution having a polymer concentration of 0.5 g / dl in concentrated sulfuric acid having a concentration of 98% was 3.4.
- IV intrinsic viscosity
- this Technola (trademark) powder was mixed with 950 g of N-methyl-2-pyrrolidone (NMP) and 20 g of calcium chloride at room temperature and allowed to stand overnight to obtain an aramid solution having a concentration of 3% by weight.
- NMP N-methyl-2-pyrrolidone
- the obtained film of 40 ⁇ m in thickness was wound on a stainless steel rod of 2 mm in diameter, and a 180 ° bending test was repeated 10 times, but no damage or cracking of the film occurred, and sufficient mechanical strength and flexibility were combined. It was a film.
- Carbon black (“Denka Black (trademark)” manufactured by Denka Co., Ltd., acetylene black, average particle diameter 35 nm) is used in place of the fine particle spherical silica of Example 1 so that the content is 20 to 95% by weight
- the slurry was obtained in the same manner as in Example 1.
- NMP was added and viscosity was adjusted.
- a high concentration particle-containing film was obtained in the same manner as in Example 1 except the above.
- the volume content of particles in this film is shown together in Table 1.
- the ratio (volume%) of the volume content is the ratio of the volume of particles to the total amount of the volume of polymer and the volume of particles present in the film.
- the obtained film with a thickness of 40 ⁇ m was wound on a stainless steel rod having a diameter of 2 mm, and a 180 ° bending test was repeated 10 times, although the film with the highest content of 95 wt% There was no damage or cracking including the film, and it was a film having sufficient mechanical strength and flexibility.
- the films 2-6 and 2-7 having a large content of particles which are examples, are comparative examples 2-1 to 2- Compared with 5, the electrical resistance hardly changed. This is considered to be because contact between particles occurs between almost all contained carbon black particles.
- Comparative Examples 3-0 to 3-2, Example 3-3 In Comparative Examples 3-0 to 3-2 and Example 3-3, LOI (limit oxygen index) of a film containing no particles and a film containing a high concentration of particles when the particles to be contained are changed from fine spherical silica to kaolin particles ), Mechanical strength and flexibility were evaluated.
- the slurry was obtained in the same manner as in Example 1 by using a ratio of 84% by weight and adding the content to be 0 to 80% by weight.
- a particle-containing film was obtained in the same manner as in Example 1 except the above.
- the volume content of particles in this film is described in Table 2.
- the ratio (volume%) of the volume content is the ratio of the volume of particles to the total amount of the volume of polymer and the volume of particles present in the film.
- each obtained film with a thickness of 40 ⁇ m was wound around a stainless steel rod having a diameter of 2 mm, and a 180 ° bending test was repeated 10 times, although the film with the highest content of 80 wt. There was no damage or cracking including other films, and it was a film having sufficient mechanical strength and flexibility.
- Example 4-1 the porosity of the high concentration particle-containing film was evaluated when the particles to be contained were changed from fine spherical silica to SiO 2 particles.
- SiO 2 particles ground product, average particle diameter 5 ⁇ m
- the weight ratio of particles is 90%, and 200 ⁇ m by the same method as Example 1.
- a thick particle-containing film was obtained.
- a large number of voids were generated between the constituting resin and SiO 2 of the inorganic particles.
- the volume content of the inorganic particles in this film was 85% by volume.
- the volume content ratio (volume%) is the ratio of the particle volume to the total of the volume of polymer and the volume of particles present in the film, and the void is the ratio of particles in the solid content excluding the content.
- a film having this high porosity was suitably used as an electrode spacing wall (separator) of a secondary battery.
- Comparative Examples 5-1 to 5-3 In Comparative Examples 5-1 to 5-3, the shape retention of the film was evaluated in the case where the resin was changed to nylon 6 polymer and fine spherical silica, carbon black and kaolin particles were used as the particles.
- Example 1 In place of the nitrogen-containing aromatic polymer of Example 1, a nylon 6 polymer was used to prepare a film using a solution having a particle content of 50% by volume, but at the drying stage on a glass plate, It was not possible to maintain the film shape.
- the inorganic particles fine spherical silica of Example 1, carbon black of Example 2, and kaolin particles of Example 3 were used.
- Examples 6-1 to 6-3 and Comparative Examples 6-4 to 6-5 In Examples 6-1 to 6-3 and Comparative Examples 6-4 to 6-5, the relationship between the viscosity of the coating liquid and the polymer concentration based on the polymer molecular weight in the coating liquid, and the high concentration particle-containing film and the porous polyethylene The air permeability and heat shrinkage of the laminate including the porous substrate and the porous polyethylene substrate were evaluated.
- Example 6-1 (Alkali treatment and molecular weight measurement of polymer) Para-based copolymerized aromatic polyamide was used as the nitrogen-containing aromatic polymer.
- the para-based copolymerized aromatic polyamide is prepared by copolymerizing (1) para-phenylenediamine, (2) copolymerized diamine, and (3) paraterephthalic acid dichloride.
- 3,4 'oxydiphenylene diamine was employ
- the polymer was added to a 5% by weight aqueous solution of sodium hydroxide, and alkali immersion treatment was performed at 130 ° C.
- NMP N-methyl-2-pyrrolidone
- the prepared dope was allowed to stand in a temperature and humidity control room (25 ° C., 50% humidity) for 1 day, and then the viscosity of the dope was measured with a viscometer (manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 3.
- the prepared dope is coated on a smooth base glass plate using a coating bar made of stainless steel, then dried at 100 ° C. for 15 minutes to volatilize NMP to some extent, and then in a room temperature water bath The coated film was solidified by immersion for 30 minutes. After that, the water was wiped off and redried at 80 ° C. for 10 minutes to obtain a polymer film.
- the obtained polymer film was cut into a strip 10 mm wide ⁇ 50 mm long, and a tensile test was carried out using a Tentilon universal tester (RTF-1210). The tensile speed was 20 mm / min.
- the thickness and the fabric weight of the film were measured from the weight of a thickness gauge and a 5 cm square sample. The results are shown in Table 3.
- a predetermined amount of polymer obtained as described above and magnesium hydroxide as filler particles were added to NMP to prepare a coating liquid.
- a compounding ratio of the polymer and the filler particles in the coating liquid 20% by weight of the polymer and 80% by weight of the filler particles were used.
- the polymer concentration (% by weight) in the coating liquid was a concentration to be 1,000 mPa ⁇ S, which is a coatable viscosity.
- the coating solution described above was added at the timing immediately before the polyethylene porous substrate (Toray Industries F10CF1; hereinafter, sometimes referred to as "PE porous film") is fed by a gripping roller, and coated onto the substrate . Then, the coating layer is solidified by immersing in a water bath for 3 minutes, and then dried in a dryer at 60 ° C. for 10 minutes, and Example of a configuration in which the particle-containing polymer layer is coated on the substrate surface was obtained.
- PE porous film Toray Industries F10CF1; hereinafter, sometimes referred to as "PE porous film”
- Example 6-2 The polymer film and laminate of Example 6-2 were produced in the same manner as in Example 6-1 except that the alkali immersion treatment time was changed to 2 hours to further accelerate polymer decomposition by alkali.
- the physical properties of the film and laminate were measured in the same manner as in Example 6-1, and the results are shown in Table 3.
- Embodiment 6-3 A polymer film and a laminate of Example 6-3 were produced in the same manner as in Example 6-1 except that the alkali concentration was changed to 1% by weight and the condition was set to promote milder polymer decomposition by alkali. did.
- the physical properties of the film and laminate were measured in the same manner as in Example 6-1, and the results are shown in Table 3.
- Comparative Example 6-4 A polymer film and a laminate of Comparative Example 6-4 were produced in the same manner as in Example 6-1 except that a polymer before alkali treatment was employed. The physical properties of the film and laminate were measured in the same manner as in Example 6-1, and the results are shown in Table 3.
- Comparative Example 6-5 The polyethylene porous substrate was used as a sample of Comparative Example 6-5.
- the tensile strength is also obtained at a level (Example 6-2) in which the number average molecular weight is reduced to about 8% of the original (Comparative Example 6-4).
- the strength retention rate was maintained at 70% or more.
- the elongation at break tends to decrease as the molecular weight decreases, but the handleability has toughness that does not pose a problem. This is considered to be an effect by the use of para-based copolyaromatic polyamide. That is, since a copolymerized diamine component functions as a soft segment, a high elongation film can be obtained, so sufficient toughness is ensured because of the original high extensibility even if the elongation at break slightly decreases due to the reduction in molecular weight. I think that I can do it.
- Para-based copolymerized aromatic polyamides are superior in at least elongation compared to para-based aromatic polyamides such as poly-p-phenylene terephthalamide (PPTA) containing no copolymerized diamine component.
- PPTA poly-p-phenylene terephthalamide
- Gurley measurement Gurley measurement of each laminate was performed according to JIS P8117 (Gurley air permeability measurement method). A value obtained by subtracting the Gurley value of the polyethylene porous substrate of Comparative Example 6-5 from the measurement value of each of the laminates of Examples 6-1 to 6-3 and Comparative Example 6-4 was taken as a ⁇ Gurley value. Moreover, what divided this delta Gurley value by coating thickness was made into delta Gurley value per unit thickness. The results are shown in Table 3. In addition, as a general term of each of these parameters, it may be described only as "a matter regarding a Gurley value" hereafter.
- the thermal shrinkage of the polyethylene porous substrate is lowered by coating the particle-containing para-copolymerized aromatic polyamide layer, and the degree thereof increases as the molecular weight of the para-copolymer aromatic polyamide decreases. It was confirmed.
- the matter related to the Gurley value and the reason for the reduction of the thermal contraction rate are relatively low by using relatively low molecular weight polymers by particles contained in a high concentration in the particle-containing para-based copolymerized aromatic polyamide layer. We believe that it is due to uniform dispersion.
- the high concentration particle-containing film of the present invention thus obtained contains a high concentration of particles, and is a polymer excellent in heat resistance. Therefore, such a film alone or a laminate comprising the film It becomes possible to use suitably for various uses by composition etc. For example, it can be suitably used as a partition between conductive members in electric and electronic components. Furthermore, it is also possible to further impart high flame retardancy by selecting particles and a polymer.
- the high concentration particle-containing film of the present invention contains particles in a high concentration, it is possible to suppress heat generation and ignition at the time of short circuit, and is suitably used for a secondary battery having a large electric capacity.
- a large amount of particles can ensure performance such as conductivity, high inter-electrode shielding performance, and low internal resistance, and can be effectively utilized as a separator that is a partition material between electrodes, particularly a separator of a secondary battery.
- Such separators are particularly useful as members for small-size, light-weight, high-capacity, high-performance batteries that can withstand long-term storage, capacitors, and electric double layer capacitors.
- the high concentration particle-containing film of the present invention has a low content of the polymer component and also has flexibility, it is preferably used for applications in which the polymer component is fired and used. For example, it is effectively used as a ceramic substrate of electronic devices.
- the high concentration particle-containing film of the present invention does not need to have a complicated configuration such as coating because it contains a large amount of particles inside, and it has become possible to effectively suppress the occurrence of warpage etc. .
- the particles metal particles or the like excellent in thermal conductivity can also be used, and they are suitably used as a heat sink or the like.
- ⁇ Aspect 1> A high concentration particle-containing film comprising a polymer component mainly comprising a nitrogen-containing aromatic polymer and containing 55% by volume or more of particles.
- ⁇ Aspect 2> The high concentration particle-containing film according to aspect 1, wherein the nitrogen-containing aromatic polymer contains an oxydiphenylene component.
- ⁇ Aspect 3> The high concentration particle-containing film according to aspect 1 or 2, wherein the nitrogen-containing aromatic polymer is a copolymerized aromatic polyamide.
- ⁇ Aspect 4> The high concentration particle-containing film according to any one of Embodiments 1 to 3, wherein the particles are inorganic particles.
- the treatment solution is a solution in which the polymer and particles are dissolved in an organic solvent, the polymer in the treatment solution is mainly a nitrogen-containing aromatic polymer, and the ratio of particles to the solid content in the treatment solution is 66% by weight
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Abstract
Description
パラフェニレンジアミン、共重合ジアミン、及びパラテレフタル酸ジクロリドを共重合させたパラ系共重合芳香族ポリアミド、並びに
粒子を含み、
前記共重合ジアミンが、全ジアミン成分に占める重量割合で25~75重量%の範囲にあり、かつ、前記粒子が、55体積%以上含まれており、
前記共重合ジアミンが、3,3’オキシジフェニレンジアミン、3,4’オキシジフェニレンジアミン、又は4,4’オキシジフェニレンジアミンである、
高濃度粒子含有フィルム。
〈態様2〉
前記粒子の含有量が、55体積%~98体積%である、態様1に記載のフィルム。
〈態様3〉
前記パラ系共重合芳香族ポリアミドの数平均分子量が、1万~15万である、態様1又は2に記載のフィルム。
〈態様4〉
前記パラ系共重合芳香族ポリアミドの数平均分子量が、2万~8万である、態様3に記載のフィルム。
〈態様5〉
前記パラ系共重合芳香族ポリアミドの固有粘度が、98%濃度の濃硫酸中、ポリマー濃度0.5g/dlの溶液について30℃で測定した固有粘度として、1.5~2.6である、態様1~4のいずれか一項に記載のフィルム。
〈態様6〉
前記粒子が無機粒子である、態様1~5のいずれか一項に記載のフィルム。
〈態様7〉
態様1~6のいずれか一項に記載のフィルム、及び基材を含む、積層体。
〈態様8〉
前記基材が、不織布又は多孔質フィルムである、態様7に記載の積層体。
〈態様9〉
態様1~6のいずれか一項に記載のフィルムを含む、リチウムイオン二次電池用セパレータ。
〈態様10〉
パラ系共重合芳香族ポリアミド、粒子、及び有機溶剤を含む処理溶液であって、該処理溶液における前記パラ系共重合芳香族ポリアミド及び前記粒子の固形分に占める該粒子の割合が、66重量%以上である、処理溶液を、基材上に適用してフィルム化する、態様1~6のいずれか一項に記載のフィルムの製造方法。
〈態様11〉
パラ系共重合芳香族ポリアミド、粒子、及び有機溶剤を含む処理溶液であって、該処理溶液における前記パラ系共重合芳香族ポリアミド及び前記粒子の固形分に占める該粒子の割合が、66重量%以上である、処理溶液を、基材上に適用して一体化する、態様7又は8に記載の積層体の製造方法。
〈態様12〉
前記処理液の固形分に占める前記粒子の割合が、75~99重量%である、態様10又は11に記載の製造方法。
〈態様13〉
態様7又は8に記載の積層体を含む、リチウムイオン二次電池用セパレータ。
〈態様14〉
態様1~6のいずれか一項に記載のフィルム、又は態様7若しくは8に記載の積層体のリチウムイオン二次電池のセパレータとしての使用。
〈含窒素芳香族ポリマー〉
本発明の高濃度粒子含有フィルムは、ポリマー成分が主として含窒素芳香族ポリマーからなり、粒子を55体積%以上含有するものである。本発明の高濃度粒子含有フィルムは、そのフィルム形態を主としてポリマー成分が保持しているものであるが、ポリマー成分の主成分、好ましくは70体積%以上、特には90体積%以上が、含窒素芳香族ポリマーから構成されていることが好ましい。
例えば含窒素芳香族ポリマーがパラ系共重合芳香族ポリアミドである場合には、有機溶媒への溶解性及び溶液の安定性の観点から、そのパラ系共重合芳香族ポリアミドが、(1)パラフェニレンジアミン、(2)共重合ジアミン、(3)パラテレフタル酸ジクロリドにて構成されるものであることが好ましい。この共重合ジアミンとして、3,3’オキシジフェニレンジアミン、3,4’オキシジフェニレンジアミンまたは4,4’オキシジフェニレンジアミンを挙げることができる。さらには特に(2)の共重合ジアミン成分として、分子鎖の屈曲性の高い3,4’オキシジフェニレンジアミンまたは4,4’オキシジフェニレンジアミンを含有することが、最も好ましい。
上述した数平均分子量及び分子量分布の少なくとも一つを有するパラ系共重合芳香族ポリアミドは、係る芳香族ポリアミドを得るときの重合の制御によって調製してもよく、又は分子量の大きいパラ系共重合芳香族ポリアミドを低分子量化することで調製してもよい。前者の重合の制御による方法では、通常の分子量のパラ系共重合芳香族ポリアミドの製造プロセスを大きく変更することが必要になることに加え、分子量の細やかな制御が困難であることから、後者の低分子量化処理による方法が好ましい。
粒子としては、ポリマーと混合した際に溶解せず、粒子形状を保つものであれば特に限定はない。さらには無機粒子や溶解しにくい結晶性のポリマーのような有機粒子であることが好ましい。中でも、良好な耐熱性を得る観点から、無機粒子が好ましい。粒子は単独で又は複数組み合わせて使用することができる。
このような本発明の高濃度粒子含有フィルムは、その厚さとしては300μm以下であることが好ましい。さらには用途にもよるが1~200μmの範囲にあることが好ましい。例えば、LiB、LiCなどのセパレータ耐熱コーティングとして用いる場合には、1~20μmの範囲であることが好ましく、さらには1~4μmの範囲であることが好ましい。本発明の高濃度粒子含有フィルムは高い物性を有するために、従来よりもより薄くして、その内部抵抗を減らすことが可能となった。また耐熱性も高く、セパレーター損傷時の熱暴走によるPE多孔膜等の収縮応力にも十分に対応が可能となった。
(熱収縮率)
本発明の高濃度粒子含有フィルム、又は該フィルムを備える積層体の熱収縮率は、得られたサンプルを一定寸法で切り出し、所定の温度に設定した乾燥機に入れ、加熱乾燥前後の寸法変化から求めることができる。本発明の高濃度粒子含有フィルムの熱収縮率としては、例えば、150℃の熱処理前における厚さ20μmのフィルムに関し、10%以下、5%以下、又は2%以下と規定することができる。また、例えば、150℃の熱処理前における、厚さ4μmのフィルム及び厚さ10μmのポリエチレン多孔質基材(東レ株式会社製F10CF1)を備える積層体の熱収縮率に関しては、50%以下、40%以下、30%以下、25%以下、又は20%以下と規定することができる。ここで、係る熱収縮率は、基材の送り出し方向に対して平行方向(MD)及び垂直方向(TD)の二方向のうちの少なくとも一方の値を意図している。
ガーレー測定は、JIS P8117(ガーレー式透気度測定法)に準じて実施した。係る測定におけるサンプルとしては、例えば、高濃度粒子含有フィルムを適用した多孔質基材からなる積層体のサンプルを使用することができる。この場合、係るサンプルの測定値から多孔質基材のガーレー値を差し引いた値を、Δガーレー値とすることができる。また、係るΔガーレー値をフィルム厚で除したものを、単位厚さ当たりのΔガーレー値とすることができる。本発明の高濃度粒子含有フィルムに関するΔガーレー値としては、65秒/100cc以下、60秒/100cc以下、又は55秒/100cc以下と規定することができる。また、本発明の高濃度粒子含有フィルムに関する単位厚さ当たりのΔガーレー値としては、30秒/100cc/μm以下、25秒/100cc/μm以下、又は20秒/100cc/μm以下と規定することができる。
そしてこのような本発明の高濃度粒子含有フィルムは、もう一つの本発明である高濃度粒子含有フィルムの製造方法によって得ることができる。すなわち、処理溶液が粒子と有機溶剤中に溶解したポリマーとを含む溶液であり、処理溶液中のポリマーが主として含窒素芳香族ポリマーであり、処理溶液中の固形分含有量に占める粒子の割合が66重量%以上であって、該処理溶液を基材上に適用してフィルム化することを特徴とする製造方法である。処理溶液中の粒子の含有量としては、乾燥後のポリマーと粒子の合計量の66重量%以上であることが必要であるが、さらには75~99重量%、特には80~95重量%の範囲が好ましい。
実施例1では、高濃度粒子含有フィルムの多孔性、機械強度及び柔軟性を評価した。
含窒素芳香族ポリマーとしてパラ系共重合芳香族ポリアミドを使用した。すなわち、(1)パラフェニレンジアミン、(2)共重合ジアミン、(3)パラテレフタル酸ジクロリド、で構成され、共重合ジアミン成分が3,4’オキシジフェニレンジアミンであって、共重合ジアミン成分のアミン成分中に占める割合が50重量%である帝人株式会社製の「テクノーラ(商標)」パウダーを用意した。このものをフィルムにした場合の密度は1.39g/cm3であった。また、98%濃度の濃硫酸中、ポリマー濃度0.5g/dlの溶液について30℃で測定した固有粘度(IV)は、3.4であった。
上記の3重量%のアラミド溶液100gを採取し、微粒球状シリカ(扶桑化学工業株式会社製、「クォートロン(商標) SP-03F」、平均粒子径0.3μm、真比重2.2)を12g添加し、株式会社シンキー製「練太郎」を用いて分散、脱泡を行い、スラリーとした。スラリー中での、アラミド樹脂:シリカ粒子の存在比は、重量比で20:80となる。
得られたスラリーを、平滑な基材であるガラス板の上に、ステンレス製の塗工バーを用いて塗工し、その後70℃で4時間乾燥してフィルムを得た。次いで得られたフィルムをイオン交換水中にて1昼夜浸漬し、NMPおよび塩化カルシウムを抽出洗浄し、粒子を74体積%含有するアラミド凝固フィルムを得た。さらに得られたフィルムを固定枠に、後の乾燥工程にて収縮が発生しないように固定し、70℃、24時間の乾燥、さらに100℃、24時間の真空乾燥を行い、高濃度粒子含有フィルムを得た。このフィルムを構成するポリマーと粒子の間には微細な多数の空隙があった。図1~図3に電子顕微鏡写真を示した。
比較例2-1~2-5、実施例2-6、2-7では、含有させる粒子を微粒球状シリカからカーボンブラックに変更した場合の高濃度粒子含有フィルムの機械強度、柔軟性及び電気抵抗を評価した。
比較例3-0~3-2、実施例3-3では、粒子を含有しないフィルム、及び含有させる粒子を微粒球状シリカからカオリン粒子に変更した場合の高濃度粒子含有フィルムのLOI(限界酸素指数)、機械強度及び柔軟性を評価した。
実施例4-1では、含有させる粒子を微粒球状シリカからSiO2粒子に変更した場合の高濃度粒子含有フィルムの多孔性を評価した。
比較例5-1~5-3では、樹脂をナイロン6ポリマーに変更し、かつ、粒子として微粒球状シリカ、カーボンブラック及びカオリン粒子を採用した場合のフィルムの形状保持性を評価した。
実施例6-1~6-3、比較例6-4~6-5では、塗工液中のポリマー分子量に基づく塗工液粘度とポリマー濃度との関係、並びに高濃度粒子含有フィルムとポリエチレン多孔質基材とを含む積層体、及びポリエチレン多孔質基材の通気性及び熱収縮率を評価した。
(ポリマーのアルカリ処理及び分子量測定)
含窒素芳香族ポリマーとしてパラ系共重合芳香族ポリアミドを使用した。係るパラ系共重合芳香族ポリアミドは、(1)パラフェニレンジアミン、(2)共重合ジアミン、(3)パラテレフタル酸ジクロリドを共重合して調製した。ここで、共重合ジアミンとしては、3,4’オキシジフェニレンジアミンを採用し、また、共重合ジアミン成分の全ジアミン成分中に占める割合は、50重量%であった。当該ポリマーを5重量%の水酸化ナトリウム水溶液中に添加し、赤外線加熱式ミニカラー染色機(株式会社テクサム技研製)にて130℃で1時間アルカリ浸漬処理を実施した。処理後のポリマーは水洗により中和され、当該ポリマーの数平均分子量を、以下の測定条件によるゲル浸透クロマトグラフィー(GPC)によって測定した。その結果を表3に示す。
カラムオーブン :CTO-20A
移動相 :NMP
オートサンプラ :SIL-20AHT
LCワークステーション:LC solution
流量 :0.3ml/分
示差屈折計検出器 :RID-10A
オーブン温度 :60℃
分子量標準試料 :ポリスチレン
上記アルカリ処理及び洗浄後のポリマーを、N-メチル-2-ピロリドン(NMP)中にポリマー濃度が3重量%となるよう添加し、80℃下で撹拌した。ポリマーがNMPにて膨潤したことを確認し、塩化リチウムを全溶液の0.8重量%となるよう添加し、ポリマーをNMP中に溶解させた溶液(以下「ドープ」という。)を作製した。作製したドープを調温・調湿室(25℃、湿度50%)にて1日静置し、その後、粘度計(東機産業株式会社製)にてドープ粘度を測定した。その結果を表3に示す。
作製したドープを、平滑な基材であるガラス板の上に、ステンレス製の塗工バーを用いて塗工し、その後、100℃で15分間乾燥してNMPをある程度揮発させ、常温水浴中に塗工フィルムを30分間浸漬して凝固させた。その後、水分を拭き取り、80℃で10分間再乾燥し、ポリマーフィルムを得た。得られたポリマーフィルムを幅10mm×長さ50mmの短冊状にカットし、テンシロン万能試験機(RTF-1210)を用いて引張試験を実施した。なお、引張速度は20mm/minとした。また、フィルムの厚み及び目付は、厚み計及び5cm角サンプルの重量より測定した。これらの結果を表3に示す。
上記のようにして得たポリマー、及びフィラー粒子として水酸化マグネシウムをNMP中に所定量添加して塗工液を調製した。ここで、塗工液中のポリマー及びフィラー粒子の配合割合としては、ポリマーを20重量%及びフィラー粒子を80重量%とした。塗工液中のポリマー濃度(重量%)は、コーティング可能な粘度である1,000mPa・Sとなる濃度とした。
ポリエチレン多孔質基材(東レ社製F10CF1。以下、「PE多孔膜」という場合がある。)を把持ローラーで送る直前のタイミングで、上述した塗工液を添加し、基材上へ塗工した。その後、水浴に3分間浸漬させて塗工層を凝固させ、その後、60℃の乾燥機中で10分間乾燥させ、基材表面に粒子含有ポリマー層が塗工された構成の実施例6-1の積層体を得た。
アルカリ浸漬処理時間を2時間に変更し、アルカリによるポリマー分解をさらに促進させたこと以外は、実施例6-1と同様にして、実施例6-2のポリマーフィルム及び積層体を作製した。係るフィルム及び積層体の物性を実施例6-1と同様に測定し、その結果を表3に示す。
アルカリ濃度を1重量%に変更し、アルカリによるポリマー分解がよりマイルドに進行する条件としたこと以外は、実施例6-1と同様にして、実施例6-3のポリマーフィルム及び積層体を作製した。係るフィルム及び積層体の物性を実施例6-1と同様に測定し、その結果を表3に示す。
アルカリ処理前のポリマーを採用したこと以外は、実施例6-1と同様にして、比較例6-4のポリマーフィルム及び積層体を作製した。係るフィルム及び積層体の物性を実施例6-1と同様に測定し、その結果を表3に示す。
ポリエチレン多孔質基材を比較例6-5のサンプルとした。
表3に示すように、アルカリ浸漬処理によりポリマーの分子量は低減し、ドープ粘度を効果的に下げられることを確認した。また、アルカリ処理時間又はアルカリ濃度により、分解後のポリマー分子量を適宜制御可能であることも確認した。
(熱収縮率測定)
各積層体を一定寸法で切り出し、所定の温度に設定した乾燥機に入れ、加熱乾燥前後の寸法変化から熱収縮率を測定した。なお、熱収縮率の測定は、基材の送り出し方向に対して平行方向(MD)及び垂直方向(TD)の二方向でそれぞれ実施した。その結果を表3に示す。
各積層体のガーレー測定は、JIS P8117(ガーレー式透気度測定法)に準じて実施した。実施例6-1~6-3、比較例6-4の各積層体の測定値から比較例6-5のポリエチレン多孔質基材のガーレー値を差し引いた値を、Δガーレー値とした。また、係るΔガーレー値を塗工厚で除したものを、単位厚さ当たりのΔガーレー値とした。その結果を表3に示す。なお、これらの各パラメーターの総称として、以下単に「ガーレー値に関する事項」と表記する場合がある。
表3に示すように、ポリマーの低分子量化により、同一ドープ粘度条件(1,000mPa・S)下において、より高いポリマー濃度を設定できることを確認した。
〈態様1〉
ポリマー成分が主として含窒素芳香族ポリマーからなり、粒子を55体積%以上含有することを特徴とする高濃度粒子含有フィルム。
〈態様2〉
含窒素芳香族ポリマーがオキシジフェニレン成分を含有する態様1記載の高濃度粒子含有フィルム。
〈態様3〉
含窒素芳香族ポリマーが共重合芳香族ポリアミドである態様1または2記載の高濃度粒子含有フィルム。
〈態様4〉
粒子が無機粒子である態様1~3のいずれか1項記載の高濃度粒子含有フィルム。
〈態様5〉
処理溶液が有機溶剤中にポリマーと粒子とを溶解した溶液であり、処理溶液中のポリマーが主として含窒素芳香族ポリマーであり、処理溶液中の固形分含有量に占める粒子の割合が66重量%以上であって、該処理溶液を基材上に静置してフィルム化することを特徴とする高濃度粒子含有フィルムの製造方法。
Claims (12)
- パラフェニレンジアミン、共重合ジアミン、及びパラテレフタル酸ジクロリドを共重合させたパラ系共重合芳香族ポリアミド、並びに
粒子を含み、
前記共重合ジアミンが、全ジアミン成分に占める重量割合で25~75重量%の範囲にあり、かつ、前記粒子が、55体積%以上含まれており、
前記共重合ジアミンが、3,3’オキシジフェニレンジアミン、3,4’オキシジフェニレンジアミン、又は4,4’オキシジフェニレンジアミンである、
高濃度粒子含有フィルム。 - 前記粒子の含有量が、55体積%~98体積%である、請求項1に記載のフィルム。
- 前記パラ系共重合芳香族ポリアミドの数平均分子量が、1万~15万である、請求項1又は2に記載のフィルム。
- 前記パラ系共重合芳香族ポリアミドの数平均分子量が、2万~8万である、請求項3に記載のフィルム。
- 前記パラ系共重合芳香族ポリアミドの固有粘度が、98%濃度の濃硫酸中、ポリマー濃度0.5g/dlの溶液について30℃で測定した固有粘度として、1.5~2.6である、請求項1~4のいずれか一項に記載のフィルム。
- 前記粒子が無機粒子である、請求項1~5のいずれか一項に記載のフィルム。
- 請求項1~6のいずれか一項に記載のフィルム、及び基材を含む、積層体。
- 前記基材が、不織布又は多孔質フィルムである、請求項7に記載の積層体。
- 請求項1~6のいずれか一項に記載のフィルムを含む、リチウムイオン二次電池用セパレータ。
- パラ系共重合芳香族ポリアミド、粒子、及び有機溶剤を含む処理溶液であって、該処理溶液における前記パラ系共重合芳香族ポリアミド及び前記粒子の固形分に占める該粒子の割合が、66重量%以上である、処理溶液を、基材上に適用してフィルム化する、請求項1~6のいずれか一項に記載のフィルムの製造方法。
- パラ系共重合芳香族ポリアミド、粒子、及び有機溶剤を含む処理溶液であって、該処理溶液における前記パラ系共重合芳香族ポリアミド及び前記粒子の固形分に占める該粒子の割合が、66重量%以上である、処理溶液を、基材上に適用して一体化する、請求項7又は8に記載の積層体の製造方法。
- 前記処理液の固形分に占める前記粒子の割合が、75~99重量%である、請求項10又は11に記載の製造方法。
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EP18823653.3A EP3647372A4 (en) | 2017-06-28 | 2018-06-27 | FILM CONTAINING HIGH CONCENTRATION PARTICLES AND ITS PRODUCTION PROCESS |
US16/626,720 US20200247964A1 (en) | 2017-06-28 | 2018-06-27 | High-concentration particle-containing film and method for producing same |
US17/984,328 US20230151165A1 (en) | 2017-06-28 | 2022-11-10 | High-concentration particle-containing film and method for producing same |
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US17/984,328 Division US20230151165A1 (en) | 2017-06-28 | 2022-11-10 | High-concentration particle-containing film and method for producing same |
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EP (1) | EP3647372A4 (ja) |
JP (1) | JP7018945B2 (ja) |
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Cited By (5)
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CN110429227A (zh) * | 2019-07-03 | 2019-11-08 | 莱州联友金浩新型材料有限公司 | 一种纤维型锂离子电池隔膜的制备方法 |
JP2020023633A (ja) * | 2018-08-08 | 2020-02-13 | 帝人株式会社 | 含窒素芳香族ポリマーフィルム |
JP2020158640A (ja) * | 2019-03-27 | 2020-10-01 | 帝人株式会社 | パラ型全芳香族ポリアミドフィルム、及びその製造方法、並びに該フィルムを含むセパレータ |
JP2021014525A (ja) * | 2019-07-12 | 2021-02-12 | 帝人株式会社 | パラ型全芳香族ポリアミド積層膜及び該積層膜が積層された積層多孔質膜 |
JP2021095663A (ja) * | 2019-12-19 | 2021-06-24 | 帝人株式会社 | パラ型全芳香族ポリアミド繊維及びその製造方法、並びにパラ型全芳香族ポリアミド樹脂塗工液の製造方法 |
Families Citing this family (2)
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JP7186603B2 (ja) * | 2018-12-25 | 2022-12-09 | 帝人株式会社 | セパレータ用コーティング液、セパレータの製造方法、及び該製造方法から得られたセパレータ |
CN112694610B (zh) * | 2020-12-16 | 2022-05-27 | 烟台泰和新材料股份有限公司 | 一种改性对位芳纶聚合液、涂覆浆料、锂电池隔膜及其制备方法 |
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- 2018-06-27 WO PCT/JP2018/024437 patent/WO2019004303A1/ja unknown
- 2018-06-27 EP EP18823653.3A patent/EP3647372A4/en active Pending
- 2018-06-27 US US16/626,720 patent/US20200247964A1/en not_active Abandoned
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JP2020023633A (ja) * | 2018-08-08 | 2020-02-13 | 帝人株式会社 | 含窒素芳香族ポリマーフィルム |
JP7184563B2 (ja) | 2018-08-08 | 2022-12-06 | 帝人株式会社 | 含窒素芳香族ポリマーフィルム |
JP2020158640A (ja) * | 2019-03-27 | 2020-10-01 | 帝人株式会社 | パラ型全芳香族ポリアミドフィルム、及びその製造方法、並びに該フィルムを含むセパレータ |
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Also Published As
Publication number | Publication date |
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KR102390741B1 (ko) | 2022-04-25 |
CN110799595A (zh) | 2020-02-14 |
EP3647372A1 (en) | 2020-05-06 |
CN110799595B (zh) | 2022-04-26 |
US20230151165A1 (en) | 2023-05-18 |
EP3647372A4 (en) | 2021-04-28 |
JPWO2019004303A1 (ja) | 2020-03-19 |
US20200247964A1 (en) | 2020-08-06 |
KR20200010459A (ko) | 2020-01-30 |
JP7018945B2 (ja) | 2022-02-14 |
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