JP2006066355A - Separator for electronic component and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a separator for an electronic component never causing a short circuit although being formed of a thin film and having high ion conductivity, extremely excellent in workability and productivity, and capable of realizing extremely high safety; and to provide its manufacturing method. <P>SOLUTION: This separator for an electronic component includes a porous structure and contains two or more kinds of filler particles different in average particle diameter. When it is assumed that the average diameters of the filler particles are a, b, c, ..., m and n in descending order, a relationship between the average particle diameters adjacent to each other is b≥ä(2√3-3)/3}a, c≥ä(2√3-3)/3}b, ..., n≥ä(2√3-3)/3}m, and the separator preferably includes a sheet-like porous base material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a separator used for an electronic component, for example, a lithium secondary battery such as a lithium ion secondary battery or a polymer lithium secondary battery, or an electric double layer capacitor, and a method for producing the separator.

  In recent years, regardless of industrial equipment and consumer equipment, demand for electrical / electronic equipment and development of hybrid vehicles has greatly increased demand for lithium-ion secondary batteries and polymer lithium secondary batteries, which are electronic components. In addition, with the diversification of the above uses, there is an increasing need for higher capacity lithium batteries and electric double layer capacitors capable of rapid charge / discharge. These electric and electronic devices are steadily becoming smaller and more functional, and in particular, lithium ion secondary batteries and polymer lithium secondary batteries are also required to be smaller and more functional.

  The lithium ion secondary battery and the polymer lithium secondary battery are a positive electrode in which an active material, a lithium-containing oxide, and a binder such as polyvinylidene fluoride are mixed with 1-methyl-2-pyrrolidone to form a sheet on an aluminum current collector. A negative electrode formed by mixing a carbonaceous material capable of inserting and extracting lithium ions and a binder such as polyvinylidene fluoride with 1-methyl-2-pyrrolidone into a sheet on a copper current collector, and a porous electrolyte membrane, An electrode body formed by winding or laminating a positive electrode, an electrolyte membrane, and a negative electrode in this order is impregnated with a driving electrolyte and sealed with an aluminum case. Conventionally, polyolefin-based porous membranes and nonwoven fabrics such as polyvinylidene fluoride and polyethylene have been used as separators for the lithium ion secondary battery and polymer lithium secondary battery.

  By the way, since the lithium ion secondary battery and the polymer lithium secondary battery are miniaturized as described above, the separator is also required to be thin. However, when a conventional separator is made thin, an internal short circuit occurs between the positive electrode and the negative electrode, a shutdown effect that contributes to the safety of the battery cannot be realized, or driving that is necessary for driving electronic components In addition to the problem that the electrolytic solution cannot be sufficiently retained, problems such as a decrease in mechanical strength and a decrease in product reliability due to loss of workability and productivity in the manufacturing process occur. The shutdown here is a phenomenon in which when the temperature in the battery rises due to some abnormality, the fine pores of the separator are closed at around 140 ° C. to 150 ° C. and the current flow is stopped.

  Various proposals have been made for the purpose of solving these problems. For example, Patent Document 1 proposes that a composite film is mixed with a filler such as polyethylene particles to have a shutdown function in order to ensure safety in an environment where the battery abnormally generates heat and overcharge. ing. And specifically, it is described that after impregnating and applying a vinylidene fluoride resin-containing coating solution to a nonwoven fabric to which polyethylene particles are adhered, it is immersed in a solvent aqueous solution to solidify, and the solvent is removed. . However, in Patent Document 1, no consideration is given to the particle size of the fine particles, and a sufficient shutdown effect cannot be expected. In addition, the voids between the filler particles are not considered. Furthermore, when the voids between the particles are large, there is a problem of causing problems such as micro shorts.

  In addition, there is a method of extracting and removing a plasticizer with an organic solvent in order to produce a separator made of a composite film containing filler particles, but the pores of the formed porous structure resin have a small pore size. Furthermore, there is a problem that the pores are blocked by the filler particles. Also, in the case of a method of replacing the organic solvent with another solvent without using a plasticizer, because the voids inside the composite are likely to be large, even if filler particles such as polyethylene melt in a certain temperature range, In addition to the problems that the gaps cannot be filled evenly and the shutdown function is not sufficiently exhibited, there are problems such as the occurrence of micro-shorts. Therefore, when the filler particles are contained, it is necessary to quickly fill the holes at the time of melting, and it is necessary to sufficiently consider the gaps between the filler particles.

  In recent years, a shutdown function as described above may not be required for large lithium batteries and electric double layer capacitors. In such an electronic component, it is not always necessary to use the resin particles having the thermoplasticity described above, but in essence, when the gap between the filler particles is large in the thin film separator, the above-described micro-short is likely to occur. There is a problem. From this point of view, it is necessary to sufficiently consider the voids between the filler particles as described above.

JP 2003-317893 A

  The present invention has been proposed in view of the actual situation as described above, and its purpose is not to cause a short circuit even though it is a thin film, workability and productivity are extremely good, and an excellent shutdown effect. It is providing the separator for electronic components which has these, and its manufacturing method.

The separator for electronic parts of the present invention is a separator for electronic parts containing at least two kinds of filler particles having different porous structures and average particle diameters, and the average particle diameters of the filler particles are increased in the order of a, b , C,..., M, n, the relationship between adjacent average particle sizes is b ≧ {(2√3-3) / 3} a, c ≧ {(2√3-3) / 3}. b,... n ≧ {(2√3-3) / 3} m.
Moreover, the manufacturing method of the separator for electronic components of this invention is for manufacturing said separator for electronic components, The 1st manufacturing method is a sheet-like porous base material on one surface of the resin film. A coating solution containing a resin that forms a porous structure and at least a good solvent that dissolves the resin, or both a good solvent and a poor solvent, is applied on the sheet-like porous substrate. A step of drying the formed coating layer and removing the solvent to obtain a laminate in which a porous structure is formed on the surface and / or inside of the sheet-like porous substrate, and then a resin from the laminate A step of peeling the film, and including at least two kinds of filler particles having different average particle diameters in the sheet-like porous substrate and / or the coating solution in order of increasing the average particle diameter of the filler particles a, b , C, ... When m and n are set, the relationship between adjacent average particle sizes is b ≧ {(2√3-3) / 3} a, c ≧ {(2√3-3) / 3} b,. ≧ {(2√3-3) / 3} m.
In addition, the second production method is a step of applying, on one surface of a resin film, a resin that forms a porous structure and at least a good solvent that dissolves the resin or a coating solution that includes both a good solvent and a poor solvent. A step of superimposing the sheet-like porous substrate on the coating layer obtained in the above step, and then drying to remove the solvent to remove the solvent on the surface and / or inside of the sheet-like porous substrate. At least two or more types of filler particles having an average particle size different from that of the sheet-like porous substrate and / or the coating liquid. When the average particle size of the filler particles is a, b, c,..., M, n, the relationship between adjacent average particle sizes is b ≧ {(2√3-3) / 3} a, c ≧ {(2√3-3) / 3} b,... n ≧ {(2√3-3) / 3} m.
In addition, the third manufacturing method, a surplus after impregnating the sheet-like porous substrate with a coating solution containing a resin forming a porous structure and at least a good solvent or a good solvent and a poor solvent for dissolving the resin A step of removing the coating solution, and then drying to remove the solvent, or immersing it in a liquid that replaces the good solvent and the poor solvent to remove the good solvent and the poor solvent, followed by further drying. A step of removing a solvent and a liquid for substituting the poor solvent, wherein the average particle size of the filler particles includes at least two kinds of filler particles having different average particle diameters in the sheet-like porous substrate and / or the coating liquid. When the diameters are a, b, c,..., M, n, the relationship between adjacent average particle sizes is b ≧ {(2√3-3) / 3} a, c ≧ {(2√ 3-3) / 3} b, ... n ≧ {(2√3-3) / 3} m It is characterized in.

  The separator for electronic components of the present invention is a thin film and has high ion conductivity, and contains filler particles having an appropriately designed particle size, thereby producing an electrochemical element that is unlikely to cause a micro short even if it is a thin film. In particular, when used in a lithium secondary battery, it can have a good shutdown function against overcharge as required.

Hereinafter, the present invention will be described in detail.
The separator for electronic parts of the present invention is a separator for electronic parts containing at least two kinds of filler particles having different porous structures and average particle diameters, and the average particle diameters of the filler particles are increased in the order of a, b , C,..., M, n, the relationship between adjacent average particle sizes is b ≧ {(2√3-3) / 3} a, c ≧ {(2√3-3) / 3}. b,... n ≧ {(2√3-3) / 3} m.
The filler particles having such a relationship of two kinds of average particle diameters adjacent to each other are illustrated in FIG. That is, the larger the average particle diameter of the gap area S _A mean particle diameter B1 or filler particles b area S _B than that formed by the A3 or filler particles a, as shown in figure 1. Therefore, the filler particles B do not enter between the filler particles A. As a result, the gap generated between the filler particles A and the filler particles B is smaller than the gap formed only by the filler particles A, and thus it is possible to suppress the generation of through holes that lead to microshorts. In addition, since the gap between the filler particles is small, the melted filler particles can sufficiently fill the gap and have a good shutdown property. When the filler particles having an average particle diameter of b are smaller than {2√3-3} / 3} a, the filler particles having an average particle diameter of b are placed in a gap formed by the filler particles having an average particle diameter of a. Therefore, a gap formed by the filler particles having an average particle diameter of a is generated in the electronic component separator as it is, a gap between the filler particles is large, and a through hole is generated to generate a micro short.
In the present invention, in addition to the filler particles having an average particle diameter of a and the filler particles having an average particle diameter of b, a third filler particle or a fourth filler particle having a different average particle diameter may be added. Good. In such a case, the filler particles having different average particle diameters are compared in the descending order, and the relationship between adjacent filler particles may have the above relationship. That is, when the relationship between the average particle diameters of the plurality of filler particles is a>b>c>...M> n, b ≧ {(2√3-3) / 3} a, c ≧ {( 2√3-3) / 3} b... N ≧ {(2√3-3) / 3} m. In the case where the third filler particles and the fourth filler particles having different average particle diameters are added, the gap between the filler particles is further reduced, so that it is possible to suppress the generation of through-holes that lead to micro-shorts. Since the gap between the filler particles is small, the melted filler particles can sufficiently fill the gap and have a good shutdown property. The average particle diameter of the filler particles in the present invention refers to the average value of primary particles.

  In the present invention, it is preferable that at least one melting point of the filler particles is 80 ° C. or higher. When filler particles having a melting point of 80 ° C. or higher are used, a good shutdown effect can be exhibited. The cause of this is not necessarily clear, but in the conventional technology, the opening of the nonwoven fabric is sometimes several tens of μm or more, and even if particles of several tens of μm melt, the eyes are uniformly filled. In contrast to the structure of the present invention, when particles having different particle sizes are arranged, the gap that should be filled when filler particles are melted becomes narrow, so that the shutdown effect is likely to appear. it is conceivable that. The filler particles having such a melting point may be at least one kind constituting the filler particles, and the other filler particles may be those having substantially no melting point. That is, if a part of the filler particles is melted by heat, the filler particles having such a melting point can easily fill the gap formed between the other filler particles or the gap between the filler particles and the sheet-like porous substrate. is there.

  Examples of the filler particles include fillers made of resin particles such as polyethylene particles, polypropylene particles, polytetrafluoroethylene particles, and styrene particles, and inorganic particles such as silica having substantially no melting point. The filler particles may be composed only of resin particles, may be composed only of inorganic particles, or may be composed of resin particles and inorganic particles in combination.

  The separator for electronic parts of the present invention preferably includes a sheet-like porous substrate in order to improve mechanical strength. A nonwoven fabric can be mentioned as a sheet-like porous base material. The fiber that is the constituent material of the nonwoven fabric is paper made of cellulose pulp, paper made of bast fibers such as cotton, cannabis, and jute, leaf vein fibers such as manila hemp, etc., or regenerated cellulose fibers and regenerated proteins such as rayon and cupra Recycled fibers such as fibers, semi-synthetic fibers such as cellulose acetate fibers and promix, nylon aramid fibers, polyethylene terephthalate fibers, polyester fibers, acrylic fibers, polyolefin fibers such as polyethylene and polypropylene, polyvinyl alcohol fibers, polyvinyl chloride fibers, poly Vinylidene chloride fiber, vinyl chloride fiber, polyurethane fiber, polyoxymethylene fiber, polytetrafluoroethylene fiber, polyparaphenylenebenzbisthiazole fiber, polyimide fiber, polyamide fiber, glass fiber, ceramic fiber, gold Nonwoven fabric made of fibers or the like, can be mentioned woven and net product (mesh).

A nonwoven fabric can be manufactured using a well-known technique. That is, it can be produced by a wet method, a dry method, a dry pulp method, a spun bond method, a melt blow method, a flash spinning method, a tow opening method, or the like. The opening of the nonwoven fabric is preferably as small as possible for the purpose of preventing a short circuit. For that purpose, the fiber diameter of the fibers used for the nonwoven fabric is desirably as thin as possible.
That is, in the present invention, it is preferable to contain at least 1% by weight, more preferably 5% by weight or more of fibers having a denier of 0.15 or less. When the fiber having a denier of 0.15 or less is less than 1% by weight, the effect of reducing the opening is reduced, which is not preferable. However, even when the opening of the nonwoven fabric is relatively large, the filler particles of the present invention are used. Even if a fiber of 0.15 denier or less is not necessarily contained, occurrence of a short circuit can be suppressed.

  The film thickness of the sheet-like porous substrate is not particularly specified, but it is necessary to reduce the size of the electronic component, particularly when used for a lithium ion secondary battery, a polymer lithium secondary battery or an electric double layer capacitor. In order to make it possible, it is preferable to select the film thickness of the separator to be 50 μm or less, particularly in the range of 5 to 30 μm. However, even if the film thickness of the separator is 50 μm or more, the film thickness can be sufficiently reduced by performing the press treatment. On the other hand, some electronic components other than those described above do not necessarily need to be a thin film, and the thickness of the separator may be 50 μm or more. In the case of use as a thick film, two or more thin film separators of 50 μm or less can be used in an overlapping manner.

  As another sheet-like porous substrate of the present invention, there is a through hole having an average pore diameter of 50 μm or less that does not substantially have a shielding structure penetrating in the direction perpendicular to the film surface, and the average of the shortest distance between adjacent through holes A microporous resin film having a thickness of 100 μm or less can be used. The material of the microporous resin film is preferably polyolefin, polyester, polyethylene naphthalate, polyimide, polyimideamide, polyphenylsulfone, polytetrafluoroethylene, etc., but is not necessarily limited to these, and heat shrinkage is small. Moreover, as long as it does not melt | dissolve with respect to the organic solvent and ionic liquid which are used for electrolyte solution, any thing can be used. In the polyolefin resin, polyethylene and polypropylene are particularly preferably used. These resins are heat-melted in a predetermined temperature range to suppress electrochemical runaway during overcharging and overheating, and provide good safety characteristics to close the through-holes in the microporous resin film. is there. Among polyesters, polyethylene terephthalate is particularly preferably used because it does not melt in the predetermined temperature range, but has little heat shrinkage and does not cause a short circuit between electrodes even in a relatively high temperature range. In addition, polyethylene naphthalate, polytetrafluoroethylene, polyimide, polyamideimide and the like are preferably used in the present invention because they have good resistance to electrolytes and ionic fluids and good heat shrinkage resistance. it can.

FIG. 2 shows an example of the microporous resin film. 2, (a) shows a plan view of the microporous resin film, and (b) shows a cross-sectional view taken along line ZZ in (a).
In the present invention, the diameter X of the through hole 2 forming the microporous resin film 1 shown in FIG. 2 is preferably 0.01 to 50 μm, more preferably 0.1 to 30 μm. When X is less than 0.01 μm, ionic conductivity tends to be hindered. On the other hand, when X is in a range exceeding 50 μm, it is not desirable because it is likely to cause a short circuit even in a normal use environment of an electronic component even if it is combined with a porous structure described later.
In the microporous resin film used in the present invention, the shortest distance Y between the adjacent through holes is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm. When Y is less than 0.01 μm, the mechanical strength of the microporous resin film may be inferior, which may cause inconveniences such as easy breakage during winding. On the other hand, when Y exceeds 50 μm, the above-mentioned mechanical strength is not a problem, but when the hole diameter of the through hole is small, there may be a disadvantage that the ion conductivity is lowered.

  The film thickness of the microporous resin film used in the present invention is desirably 20 μm or less for battery use. This is because it is desirable to make the electrode as thick as possible in accordance with the recent demand for large capacity batteries, and the increase in capacity is required to make the separator as thin as possible. In addition, in an electronic component such as an electric double layer capacitor, when it is necessary to hold a large amount of electrolyte, it may be necessary to further increase the film thickness. The thickness design should be decided.

  In the present invention, as illustrated in FIG. 3, a configuration in which two microporous resin films 1 are arranged at a position where the through hole 2 does not directly penetrate in the vertical direction can be employed. By adopting such a configuration, it is possible to reliably stop the growth of dendrites generated during overcharge and charge / discharge cycles in at least the solid resin portion of the microporous resin film. It becomes possible to prevent not only a battery and a lithium polymer secondary battery but also a short circuit in the early stage of the charge / discharge cycle caused by dendrite generated when lithium metal is used. However, in the present invention, when two microporous resin films are stacked, the phase of the through holes may be the same and the through holes may exist simultaneously in the direction perpendicular to the separator surface. In the case of using a plurality of microporous resin films, as illustrated in FIG. 3, at least two or more types of filler particles A having a different porous structure 3 and different average particle diameters are provided between the microporous resin films 1. It is more desirable in terms of battery performance to make a contrivance such as forming an ion flow path by configuring A and B.

  The microporous resin film used in the present invention can be prepared by, for example, a method of continuously forming minute through holes with a laser, or by forming intermittent fine slits on the film in advance. It is possible to form a microporous resin film by stretching in a direction perpendicular to this direction, but it is not always necessary to use the above method.

  In the present invention, it is desirable that the melting point of the sheet-like porous substrate exceeds 180 ° C. If the melting point of the sheet-like porous substrate is 180 ° C. or less, it is likely to cause a short circuit between the electrodes because it is easily melted and contracted during heating, which may be a problem. In the present invention, if the material constituting the nonwoven fabric or microporous resin film, which is the sheet-like porous substrate, has a melting point exceeding 180 ° C., the above-described shrinkage during overheating is prevented. Therefore, it can be preferably used in the present invention. In the case of a non-woven fabric, there is no problem with shrinkage if the melting point of a part of the fibers constituting it exceeds 180 ° C. In the case of a microporous resin film, in particular, a plurality of microporous resin films For example, if one of the materials has a melting point of more than 180 ° C., shrinkage during overheating is less likely to occur.

  In the present invention, the porous structure is a solvent-soluble resin, and the sheet-like porous base material and the filler particles are made of a material that does not substantially swell up to 70 ° C. with respect to the organic electrolyte. It is preferable to include. If all the porous structures are dissolved or gelled in the organic electrolyte in the range up to 70 ° C., the ion conductivity may be inhibited under the high temperature use environment of the battery, which is not preferable. When a porous material is partially formed using a material whose swelling temperature exceeds 70 ° C., at least the porous body structure remains even under a high temperature use environment up to 70 ° C. It is preferable because it does not extremely decrease.

  In the present invention, the resin forming the porous structure is desirably a solvent-soluble resin. Furthermore, by selecting the resin used for the so-called polymer electrolyte as the material of the porous structure, the retention of the electrolyte and the extraction of the electrolyte are improved, and safety and cycle characteristics are improved. This is also preferable. In particular, the solvent-soluble resin is most preferably polyvinylidene fluoride or a vinylidene fluoride copolymer because of the various characteristics described above. When polyvinylidene fluoride resin is used, since it has good resistance to general electrolytes, it is easy to maintain porosity even when wet with electrolytes. Since it is easy to hold, it is effective in improving safety and cycle characteristics and is preferably used. In addition, if a resin copolymer such as a vinylidene fluoride-hexafluoropropylene copolymer is mixed and used, the resin swells under normal use environment, so that adhesion to the electrode is appropriately given. This also makes it possible to further improve the cycle characteristics. The copolymer is not necessarily limited to the above examples, and may be selected and used in consideration of the various characteristics described above. A plurality of types may be used in combination as in the above examples. It doesn't matter. In the present invention, the solvent-soluble resin to be used is not limited to the above-mentioned vinylidene fluoride type, and any resin that exhibits the above-mentioned advantages can be suitably used. For example, polyacrylonitrile, Any of the resins called gel electrolytes such as polyethylene oxide can be suitably used.

  Examples of the polyvinylidene fluoride include a vinylidene fluoride homopolymer or a copolymer containing vinylidene fluoride. The vinylidene fluoride homopolymer is obtained by the addition polymerization reaction of vinylidene fluoride monomer. The polymerization methods include radical polymerization, cationic polymerization, anionic polymerization, light / radiation polymerization, suspension polymerization, emulsion polymerization, solution polymerization, Examples thereof include bulk polymerization. The copolymer containing vinylidene fluoride is a resin obtained by copolymerizing vinylidene fluoride and other monomers. Examples of other monomers include hydrocarbon monomers such as ethylene and propylene, vinyl fluoride, 3 Fluorine-containing monomers such as fluorinated ethylene, ethyl trifluoride, tetrafluoroethylene, hexafluoropropylene, fluoroalkyl vinyl ether, carboxyl group-containing monomers such as monomethyl maleate and monomethyl citraconic acid, or allylglycol And epoxy group-containing vinyl monomers such as sidine ether and glycidyl crotonic acid ester. Among these, in particular, a copolymer comprising vinylidene fluoride and one or more of tetrafluoroethylene or hexafluoropropylene is preferable.

  As the resin constituting the porous structure, in addition to the above-mentioned polyvinylidene fluoride and vinylidene fluoride copolymer, polyacrylonitrile, a copolymer containing acrylonitrile, a polymethyl methacrylate, a copolymer containing methyl methacrylate , Copolymers containing polystyrene, styrene, polyethylene oxide, ethylene oxide, polyimide amide, polyphenyl sulfone, polyether sulfone, polyether ether ketone, and a copolymer containing at least one of polytetrafluoroethylene Can do. Each homopolymer is obtained by an addition polymerization reaction of monomers of each resin, and a known technique can be used as the polymerization method. That is, it can be obtained by radical polymerization, cationic polymerization, anionic polymerization, light / radiation polymerization, suspension polymerization, emulsion polymerization foam, bulk polymerization and the like. Moreover, the copolymer containing each resin is resin which copolymerized the monomer of each resin, and another monomer, and there is no prescription | regulation in particular as another monomer. These copolymers can also be obtained by the same polymerization method as the homopolymer.

  In the present invention, it is desirable that the resin constituting the porous structure is soluble in an amide solvent, a ketone solvent, or a furan solvent. The vinylidene fluoride resin particularly preferably used in the present invention has a very good film formability when dissolved in an amide solvent, and can be used particularly preferably, but improves the drying efficiency of the coated surface. Therefore, it is desirable to use a resin that is soluble in a ketone solvent or a furan solvent. In the present invention, the above solvents may be appropriately mixed and used while observing the drying rate and the film formation state.

  In the present invention, the thickness of the electronic component separator is desirably 1 to 30 μm. When it is 1 μm or less, even in the presence of the filler particles of the present invention, minute pinholes are likely to occur, and microshorts are likely to occur. On the other hand, if it is thicker than 30 μm, the internal resistance of the separator for electronic parts increases, which is undesirable because it causes the battery performance and the capacitor performance to deteriorate.

  The electrochemical element to which the separator for electronic parts of the present invention can be applied can be satisfactorily used for capacitors as well as ordinary lithium batteries. Any of the separators for electronic parts of the present invention has low air permeability, and therefore, it is possible to suppress the internal resistance as a separator for electronic parts, particularly when high rate characteristics are required. Alternatively, when characteristics at a low temperature are required, similar effects can be expected in these characteristics regardless of whether it is a battery or a capacitor. In addition, since the separator for electronic parts of the present invention does not cause a micro short even if it is a very thin film, it is possible to increase the volume of the electrode portion. Is possible.

Next, the manufacturing method of the separator for electronic components of this invention is described.
The first production method of the present invention includes a step of placing a sheet-like porous substrate on one surface of a resin film, a resin that forms a porous structure on the sheet-like porous substrate, and at least the A step of applying a good solvent for dissolving the resin or a coating solution containing both a good solvent and a poor solvent, the surface of the sheet-like porous substrate by drying the formed coating layer and removing the solvent, and / or Alternatively, the method includes a step of obtaining a laminate in which a porous structure is formed inside, and then a step of peeling a resin film from the laminate, and the average particle diameter is different from that of the sheet-like porous substrate and / or the coating solution. When at least two types of filler particles are included and the average particle size of the filler particles is a, b, c,..., M, n in order of decreasing size, the relationship between adjacent average particle sizes is b ≧ {(2√ 3-3) / 3} a, c ≧ {(2√3-3) / 3} b ,..., N ≧ {(2√3-3) / 3} m.
In addition, the second production method is a step of applying, on one surface of a resin film, a resin that forms a porous structure and at least a good solvent that dissolves the resin or a coating solution that includes both a good solvent and a poor solvent. A step of superimposing the sheet-like porous substrate on the coating layer obtained in the above step, and then drying to remove the solvent to remove the solvent on the surface and / or inside of the sheet-like porous substrate. At least two or more types of filler particles having an average particle size different from that of the sheet-like porous substrate and / or the coating liquid. When the average particle size of the filler particles is a, b, c,..., M, n, the relationship between adjacent average particle sizes is b ≧ {(2√3-3) / 3} a, c ≧ {(2√3-3) / 3} b,... n ≧ {(2√3-3) / 3} m.
In addition, the third production method may include a step of impregnating a sheet-like porous substrate with a coating solution containing a resin that forms a porous structure and at least a good solvent that dissolves the resin or both a good solvent and a poor solvent. The step of removing the excess coating solution, and then drying to remove the solvent, or immersing in a liquid that replaces the good solvent and the poor solvent to remove the good solvent and the poor solvent, followed by further drying. It has the process of removing the liquid which substitutes a good solvent and a poor solvent, and contains the at least 2 or more types of filler particle from which an average particle diameter differs in the said sheet-like porous base material and / or the said coating liquid. When the particle diameters are a, b, c,..., M, n in order of increasing particle size, the relationship between adjacent average particle diameters is b ≧ {(2√3-3) / 3} a, c ≧ {(2 √3-3) / 3} b,... N ≧ {(2√3-3) / 3} m And wherein the Rukoto.

  Examples of the resin film used in the first and second manufacturing methods include a polyolefin film and a polyester film. The resin film may be subjected to surface treatment such as mold release treatment or easy adhesion treatment. The resin film has a function of a surface protective film of the electronic component separator, and the laminate can be wound and stored and transported while the electronic component separator is held on the resin film.

  The selection of the resin film affects the properties of the separator for electronic parts formed in relation to the affinity with the coating liquid applied on the resin film and the peelability from the formed porous structure. . In the present invention, in the first and second production methods, the peel strength for peeling the resin film from the laminate is preferably from 0.1 to 75 g / 20 mm, more preferably from 0.1 to 40 g / 20 mm. That is, a tape-shaped test piece obtained by cutting out the porous structure formed on the resin film after coating and drying to a width of 20 mm was prepared, and a part of the porous structure at the end portion was prepared on the test piece. It is obtained when peeling and fixing the end of the porous structure at the end and the other non-peeled end to the upper and lower chucks of Tensilon and measuring the tension at a speed of 50 mm / sec. The tensile load for peeling is measured at five points, and the average value divided by the width of 20 mm, which is the cutout width, is taken as the evaluation value as the peeling strength.

  In the present invention, in the case of the second production method, the coating liquid is applied onto the resin film before the sheet-like porous substrate is overlaid as described above, but the peel strength of the resin film is 0.1 g / In a resin film having a relatively good releasability such as less than 20 mm, when the coating solution viscosity is low, the coating surface in a wet state immediately after coating is not stable, and the coating amount per unit area of the coating solution is Since the sheet-like porous base material is overlapped with the wet coating layer immediately after coating, the weight per unit area of the porous structure varies in the surface direction of the separator. This phenomenon is essentially derived from the surface tension of the resin film. Apart from this, when the peel strength of the resin film is less than 0.1 g / 20 mm, the separator for electronic parts may peel from the resin film in the drying step, which is not preferable. On the other hand, in a film having high adhesiveness exceeding 75 g / 20 mm, the above fluctuation is not observed, but it is not preferable because it is difficult to efficiently peel and take out the separator for electronic parts from the resin film. On the other hand, in the first production method of the present invention in which a sheet-like porous substrate is placed on a resin film and stacked, and then a coating liquid is applied thereon, the coating liquid is directly sheet-like porous. Since the coating liquid is entangled with the sheet-like porous substrate after coating because it is coated on the porous substrate, even if the peel strength of the resin film is less than 0.1 g / 20 mm, Although the coating amount variation as described above does not occur, the separator for electronic parts may be peeled off from the resin film in the drying step, which is not preferable. On the other hand, when a resin film having a peel strength exceeding 75 g / 20 mm is used, it is difficult to efficiently peel and remove the electronic component separator from the resin film, which is not preferable.

  Further, as another advantage of using a resin film having a peel strength in the above range, the following contents are important in controlling the pore diameter of the porous structure. That is, although it is common to any of the above manufacturing methods, when the peel strength is set to a low range close to 0.1 g / 20 mm, the pore diameter of the pores of the separator surface in contact with the resin film is the separator surface corresponding to the coating surface layer. In contrast, when designed in a high range close to 75 g / 20 mm, the pore diameter of the pores on the separator surface in contact with the resin film is smaller than that on the separator surface corresponding to the coating surface layer. In addition, if it is less than 0.1 g / 20 mm, the pores on the separator surface on the side in contact with the resin film may be blocked, and if it exceeds 75 g / 20 mm, the pores on the separator surface corresponding to the coating surface layer may be blocked. It becomes easy. The cause of these phenomena is not always clear, but even when materials with different surface tensions are used for the sheet-like porous substrate, the same surface asymmetry of the same pore diameter occurs, so it is caused by the strength of the surface tension. Conceivable. Therefore, in the present invention, even if the material of the sheet-like porous substrate is fixed due to the demand from the battery design, the pore diameters on both the front and back sides of the separator including the porous structure composited with the sheet-like porous substrate are determined. The symmetry can be controlled by the surface property of the resin film. In other words, in the present invention, compared to the conventional method of controlling the symmetry of the pore diameter of the pores on both the front and back surfaces by the material of the sheet-like porous substrate, by setting the peel strength of the resin film, The symmetry of the hole diameter can be controlled.

The good solvent in the first, second and third production methods of the present invention is a solvent in which the resin forming the porous structure is dissolved. When polyvinylidene fluoride resin is used as the resin, examples of good solvents include N, N-dimethylacetamide, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, N, N-dimethylsulfoxide and the like. It is done. Dispersion and dissolution of the vinylidene fluoride resin in a good solvent can be performed using a commercially available stirrer. The poor solvent is a solvent that does not dissolve the resin that forms the porous structure. As the poor solvent, a solvent having a boiling point higher than that of the good solvent is selected. Examples of the poor solvent include dibutyl phthalate, ethylene glycol, diethylene glycol, glycerin and the like. The concentration of the vinylidene fluoride resin in the coating solution can be appropriately set in consideration of the characteristics of the obtained separator.
A combination of the good solvent and the poor solvent having a large difference in azeotropic or drying temperature difference and vapor pressure is not preferable in terms of increasing the frequency of occurrence of through-holes typified by pinholes, and is desirable in terms of production efficiency. Absent. The difference in boiling point between the good solvent and the poor solvent is preferably 50 ° C. or less, particularly 30 ° C. or less, in view of production efficiency. If the temperature exceeds 50 ° C., the production process speed cannot be increased, and the drying energy increases, which is not preferable. In addition, when it exceeds 50 ° C., when drying conditions are set stepwise, instantaneous condition switching in the process direction becomes practically impossible, which is not suitable for mass production. .
In the present invention, the coating solution may contain at least two good solvents that dissolve a resin for forming a porous structure, and may contain at least one poor solvent that does not dissolve the resin. Since it is important to reduce the viscosity of the coating solution to some extent from the handling properties of the coating solution, an auxiliary good solvent having a relatively low viscosity is used in combination with a main good solvent different from this, and the coating solution viscosity It is desirable to reduce Such an auxiliary good solvent may be selected in consideration of the drying viscosity with the poor solvent and the azeotropic property between the solvents in addition to the above solvent viscosity. The auxiliary good solvent in the present invention is not limited to one type, and a plurality of types may be used.

  As a method for coating the coating liquid on a sheet-like porous substrate or resin film, coating or casting is performed by a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a gravure coating method, a screen printing method, or the like. The law etc. can be mentioned. Thereby, resin which forms a porous structure on the surface and / or inside of a sheet-like porous substrate is laminated and infiltrated. Next, the solvent is evaporated by drying from the coating solution on the coated sheet-like porous substrate to form a porous structure to obtain a laminate. Next, the resin film can be peeled from the laminate to obtain the electronic component separator of the present invention.

  In the coating liquids in the first, second and third production methods of the present invention, when a highly hygroscopic solvent is used as the solvent, it is necessary to prevent moisture from entering as much as possible. In the present invention, the coating solution preferably has a water content of 0.7% by weight or less, more preferably 0.5% by weight or less, as measured by the Karl Fischer method. If the water content exceeds 0.7% by weight, gelation progresses early and the storage period of the coating solution becomes extremely short, or the film thickness of the porous structure formed becomes extremely uneven. When the thickness is thick, the pore size becomes extremely small due to gelation of the coating liquid due to water mixing, and the proportion of pore sizes less than 0.1 μm increases. Further, since the gel shrinks when it is solidified by drying of the solvent, the portion having a thin film thickness (non-gel portion) is pulled, and the ratio of the pore diameter exceeding 15 μm is increased. Since the gel is a partial occurrence, the porous structure as a whole has a large number of pores, and as a result, the average pore size by the bubble point method exceeds 15 μm, and the average particle size of the filler particles The diameter is lower than 1% of the hole diameter. When such a large hole diameter occurs in a spot manner, micro-shorts are likely to occur in that part, while when a part with a small hole diameter is mixed as a large part, the variation in internal resistance in the surface direction is increased. This causes a variation in capacitor performance, which is a problem. Such variations tend to adversely affect cycle characteristics.

  In the first, second and third production methods of the present invention, the sheet-like porous substrate and / or the coating liquid contains at least two kinds of filler particles having different average particle diameters. In the case of filler particles composed of particles, it is preferable to perform a drying treatment under temperature conditions that do not melt the particles. Since many solvents capable of dissolving the vinylidene fluoride resin have a high boiling point, a heating temperature of 70 to 180 ° C. is substantially required. For this reason, it is only necessary to finish the drying in as short a time as possible by increasing the drying speed and further increasing the process speed while performing the drying at an early stage. When the heating temperature is lower than 70 ° C., the drying efficiency is poor and the production efficiency is not increased. On the other hand, when the temperature exceeds 180 ° C., most of the fine particles are melted, which adversely affects the provision of the shutdown function. In general, drying conditions are set in stages, and it is preferable to dry the poor solvent after drying the good solvent first, in order to form a porous structure. If not azeotroped, both solvents do not necessarily have to be separated and dried. The drying is desirably performed by determining the drying conditions while appropriately controlling the porosity and the pore diameter of the porous structure. In the present invention, the combination of the solvent formulation, the drying temperature, and the air flow rate are appropriately selected as described above, thereby realizing both the optimization of the separator shutdown function and other battery performance and the improvement of the production efficiency. be able to. Further, in the present invention, it is not necessary to provide a process for removing a poor solvent and a residual solvent using a solvent as in the above prior art, and a porous structure optimal as a separator can be obtained by passing a drying process once after coating. Can be easily produced. Therefore, since the production efficiency is very good, it is possible to provide a large amount of inexpensive and high-quality separators.

  In the present invention, any of the above production methods is preferably used. For example, when the porosity of the sheet-like porous substrate is large, the second production method is preferred. That is, in the case of the first production method, for example, in the case of a non-woven fabric constituting the sheet-like porous substrate in order to apply the coating liquid on the resin film on which the sheet-like porous substrate is stacked. This is because air tends to remain in the gaps between the fibers constituting this, which may cause a coating defect. However, in the first manufacturing method, since the sheet-like porous substrate can be wound in advance coaxially with the resin film, the sheet-like porous substrate is unwound separately as in the second manufacturing method. Therefore, a more efficient production is possible because no unwinding mechanism is required. Therefore, the first production method is suitable for a sheet-like porous substrate having a relatively low porosity and no problem in film formation. The porosity of the sheet-like porous substrate should be determined with priority given to battery design, and the production method may be appropriately selected according to the design requirements. In the second production method, for example, it is possible to produce a homogeneous separator without coating defects regardless of the porosity of the sheet-like porous substrate, but any method is used. However, if a manufacturing method is selected in consideration of various physical properties of the sheet-like porous substrate represented by the above porosity, a homogeneous separator can be manufactured.

Further, in the third production method of the present invention, the sheet-like porous material is applied to a coating solution containing a resin that forms the porous structure and at least a good solvent that dissolves the resin or both a good solvent and a poor solvent. It has the process of removing an excess coating liquid after impregnating a base material. In this manufacturing method, since the sheet-like porous substrate is impregnated with the coating liquid, the coating liquid uniformly penetrates the inside of the sheet-like porous substrate, and the coating adheres to the surface with a doctor blade or the like. A uniform separator having a very thin porous structure of about 1 to 2 μm on each of the front and back surfaces is obtained by drying the liquid after scraping off the liquid to make the coating liquid remaining on the front and back surfaces extremely thin. Obtainable. When the surface layer is very thin as described above, after impregnation and scraping, the sheet-like porous substrate that is wet with the coating solution is immersed in a liquid that replaces the good solvent and the poor solvent. Thus, a uniform separator can be obtained by replacing the good solvent and the poor solvent with the replacement liquid. Examples of the replacement liquid include ion exchange water.
According to the study by the present inventors, for example, when polyvinylidene fluoride is used as a resin for forming a porous structure, a skin layer is formed on the surface of the separator in the solvent replacement method when the amount of coating is large. However, there was a case where the problem that the air permeability becomes high may occur. However, as described above, the coating layer remaining on the surface layer of the separator is about 1 to 2 μm on one side and 2 on both sides as a guide after removing the solvent. If it is about -4 micrometers, it is hard to produce a skin layer also by said solvent substitution method, Therefore It is possible to obtain the uniform separator which has low air permeability. In addition, as described above, when an extremely thin porous structure is formed, the amount of solvent in the coating liquid to be solvent-substituted is small, so that the processing of the extracted solvent is relatively easy. Is also an advantage.

  All of the separators for electronic parts of the present invention obtained by the first, second and third manufacturing methods described above have low air permeability, and in particular, lithium-based batteries that are required to have high rate characteristics and low temperature characteristics. In particular, it can be suitably used for capacitors for power applications.

  Below, the separator for electronic parts of the present invention will be described with reference to examples. However, the present invention is not limited to these examples.

A vinylidene fluoride homopolymer having a weight average molecular weight of 300,000 is dissolved in 1-methyl-2-pyrrolidone and dimethylacetamide (good solvent), dibutyl phthalate (poor solvent) is added, and the vinylidene fluoride homopolymer component is 10 weights The coating liquid adjusted so that it might become% was obtained. When the amount of water contained in this solution was measured by the Karl Fischer method, it was 0.6% by weight. Next, a polyethylene film having a primary average particle diameter of 5 μm and a melting point of 113 ° C. on a non-woven fabric having a thickness of 10 μm made of polyethylene terephthalate fiber having a melting point of 250 ° C. in advance on the resin film surface made of polyethylene terephthalate, and the same melting point The polyethylene particles having a primary average particle diameter of 1 μm were each held at 1 g / m ² , and the coating solution was applied to the nonwoven fabric by a casting method. Next, a solvent having a thickness of 18 μm having a porous structure of vinylidene fluoride homopolymer between the nonwoven fabric fibers is obtained by evaporating the solvent in the coating liquid contained inside the nonwoven fabric by heat and peeling the resin film. The separator for electronic parts of the invention was obtained. The peel strength of the resin film laminate was 17 g / 20 mm.
When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The average pore diameter of each pore was smaller than the thickness of the separator. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction.

A vinylidene fluoride homopolymer having a weight average molecular weight of 300,000 is dissolved in 1-methyl-2-pyrrolidone and dimethylacetamide (good solvent), dibutyl phthalate (poor solvent) is added, and the vinylidene fluoride homopolymer component is 5 wt. The coating liquid adjusted so that it might become% was obtained. When the amount of water contained in this coating solution was measured by the Karl Fischer method, it was 0.65% by weight. Next, a polyethylene film having a primary average particle diameter of 1 μm and a melting point of 113 ° C. and a primary average particle diameter of 0 are formed on a non-woven fabric 10 μm thick made of polyethylene terephthalate fibers having a melting point of 240 ° C. The polyethylene particles having a melting point of 132 ° C. of 3 μm and the former holding 10 g / m ^{2 and the} latter 7 g / m ² were placed, and the coating solution was applied onto the nonwoven fabric by the casting method. Next, the solvent in the coating liquid contained inside the nonwoven fabric was evaporated by heat, and the resin film was peeled off to obtain a composite membrane having a porous structure of vinylidene fluoride homopolymer between the nonwoven fabric fibers. This was subjected to press treatment to obtain a separator for electronic parts of the present invention having a thickness of 11 μm. The peel strength of the resin film laminate was 0.6 g / 20 mm.
When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The pore diameter of each pore was smaller than the thickness of the separator. Further, almost no inclination of the pore size distribution was observed in the thickness direction of the separator.

A polyamideimide resin having a weight average molecular weight of 600,000 was dissolved in dimethylacetamide (good solvent), and dibutyl phthalate (poor solvent) was added to obtain a coating solution adjusted so that the polyamideimide resin component was 10% by weight. . The amount of water contained in this coating solution was measured by the Karl Fischer method and found to be 0.5% by weight. Next, on the surface of the resin film made of polyethylene terephthalate, a 10 μm-thick nonwoven fabric made of polyethylene terephthalate fibers having a melting point of 240 ° C. in advance has a primary average particle diameter of 3 μm and a melting point of 113 ° C. polyethylene particles and a primary average particle diameter of 1 μm. Polypropylene particles having a melting point of 148 ° C. with the former held at 20 / m ² and the latter held at 10 g / m ² were placed, and the coating solution was applied onto the nonwoven fabric by the casting method. Next, the solvent in the coating liquid contained inside the nonwoven fabric is evaporated by heat, and the resin film is peeled off, thereby having a porous structure of polyamideimide resin between the nonwoven fabric fibers having a thickness of 23 μm. An electronic component separator was obtained. The peel strength of the resin film laminate was 65 g / 20 mm.
When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The pore diameter of each pore was smaller than the thickness of the separator. No inclination of the pore size distribution was observed in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction.

A vinylidene fluoride homopolymer having a weight average molecular weight of 200,000 is dissolved in 1-methyl-2-pyrrolidone and dimethylacetamide (good solvent), dibutyl phthalate (poor solvent) is added, and the vinylidene fluoride homopolymer component is 8 weights The coating liquid adjusted so that it might become% was obtained. The amount of water contained in this coating solution was measured by the Karl Fischer method and found to be 0.5% by weight. Next, a polytetrafluoroethylene particle having a primary average particle diameter of 1.5 μm and a melting point of 350 ° C. and a primary average particle diameter of 0 on a 10 μm-thick nonwoven fabric made of polyethylene terephthalate fiber in advance on the resin film surface made of polyethylene terephthalate. melting point places the polytetrafluoroethylene particles 350 ° C. which was allowed to 5 g / m ² respectively held in .5Myuemu, was the coating liquid was applied by a casting method on the nonwoven fabric. Next, the solvent in the coating liquid contained inside the nonwoven fabric was evaporated by heat, and the resin film was peeled off to obtain a composite membrane having a porous structure of vinylidene fluoride homopolymer between the nonwoven fabric fibers. This was pressed to obtain a separator for electronic parts of the present invention having a thickness of 25 μm. The peel strength of the resin film laminate was 15 g / 20 mm.
When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The pore diameter of each pore was smaller than the thickness of the separator. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction.

A polyamideimide resin having a weight average molecular weight of 300,000 was dissolved in dimethylacetamide (good solvent), and dibutyl phthalate (poor solvent) was added to obtain a coating solution adjusted so that the polyamideimide resin was 10% by weight. The amount of water contained in this coating solution was measured by the Karl Fischer method and found to be 0.51% by weight. Next, on the resin film surface made of polyethylene terephthalate, the shortest distance between adjacent through holes having an average hole diameter of 20 μm that does not substantially have a shielding structure penetrating in the direction perpendicular to the film surface is 20 μm and the thickness is 6 μm. On the surface of the porous resin film, 10 g / m ^{2 of} polytetrafluoroethylene particles having a primary average particle diameter of 5 μm and a melting point of 350 ° C., and 5 g of polytetrafluoroethylene particles having a primary average particle diameter of 2 μm and a melting point of 350 ° C. / M ² was placed, and the solution was applied onto the microporous resin film by a casting method. Next, the solvent in the coating solution applied to the microporous resin film is evaporated by heat, and the resin film is peeled off, so that the polyamideimide resin is formed on the front and back surfaces of the microporous resin film and inside the through holes. The separator for electronic parts of the present invention having a porous structure and a thickness of 10 μm was obtained. The peel strength of the resin film laminate was 16 g / 20 mm.
When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The pore diameter of each pore was smaller than the thickness of the separator. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction.

  The separator for electronic parts of the present invention is the same as in Example 1 except that part of the fibers constituting the nonwoven fabric is replaced so that the fiber diameter is 0.1 denier so that the fiber diameter becomes 10% by weight. Got. The thickness of the nonwoven fabric at this time was 10 μm. Moreover, the thickness of the obtained separator for electronic components was 20 micrometers, and the peeling strength with respect to the laminated body of a resin film was 20 g / 20mm. When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The pore diameter of each pore was smaller than the thickness of the separator. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction.

  In Example 1, a separator for an electronic component was obtained in the same manner as in Example 1 except that a part of the fibers constituting the nonwoven fabric was replaced so that the fiber diameter was 0.1 denier so that it was 50% by weight. . The thickness of the nonwoven fabric at this time was 10 μm. The thickness of the obtained separator for electronic parts was 18 μm, and the peel strength of the resin film laminate was 16 g / 20 mm. When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The pore diameter of each pore was smaller than the thickness of the separator. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction.

  In Example 1, the same coating solution as in Example 1 was applied to a resin film made of polyethylene terephthalate by direct casting, and the two polyethylenes of Example 1 were applied on the coated surface in a wet state immediately after application. The nonwoven fabric holding the particles was stacked by wet lamination. Other than that was carried out similarly to Example 1, and obtained the separator for electronic components of this invention. The thickness of the obtained separator for electronic components was 21 μm, and the peel strength of the resin film laminate was 14 g / 20 mm. When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The pore diameter of each pore was smaller than the thickness of the separator. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction.

  An electronic component separator of the present invention was obtained in the same manner as in Example 3 except that the nonwoven fabric of Example 6 was used. The thickness of the obtained separator for electronic parts was 21 μm, and the peel strength of the resin film laminate was 21 g / 20 mm. When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The diameter of each pore was smaller than the thickness of the separator. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction.

After impregnating the microporous resin film of Example 5 with the coating solution of Example 5, the front and back surfaces were both scraped with a doctor blade, immersed in ion-exchanged water, and then dried in a dryer at 80 ° C. for 1 hour. Thus, a separator for electronic parts of the present invention having a thickness of 9 μm having a porous structure of polyamideimide resin on the front and back of the microporous resin film and inside of the through hole was obtained.
When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The pore diameter of each pore was smaller than the thickness of the separator. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction.

Prepare a coating solution in which the two filler particles of Example 1 were mixed and dispersed in the coating solution of Example 3, and the nonwoven fabric was prepared in the same manner as in Example 1 except that the nonwoven fabric was not placed using this coating solution. An unused separator for electronic parts of the present invention having a thickness of 12 μm was obtained.
When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The pore diameter of each pore was smaller than the thickness of the separator. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction.

Prepare a coating solution prepared by mixing and dispersing the two types of filler particles of Example 3 in the coating solution of Example 3, and use this coating solution to place the nonwoven fabric in the same manner as in Example 1 except that the nonwoven fabric is not placed. An unused separator for electronic parts of the present invention having a thickness of 11 μm was obtained.
When this electronic component separator was observed with an electron microscope, there were no through holes such as pinholes, and the porous structure was connected to one side of the separator from the other side by a large number of pores. The pore diameter of each pore was smaller than the thickness of the separator. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction.

[Comparative Example 1]
Only a nonwoven fabric made of polyethylene terephthalate fibers having a thickness of 20 μm was used as a separator for electronic parts for comparison.
[Comparative Example 2]
In Example 1, a separator for electronic parts for comparison was obtained in the same manner as in Example 1 except that only polyethylene particles having a primary average particle diameter of 5 μm were used. The electronic component separator had a thickness of 17 μm.
[Comparative Example 3]
In Example 1, an electron for comparison was used in the same manner as in Example 1 except that instead of polyethylene particles having a primary average particle size of 1 μm, polyethylene particles having a primary average particle size of 0.05 μm and a melting point of 113 ° C. were used. A separator for parts was obtained. The thickness of this electronic component separator was 18 μm.

The characteristics of the separators for electronic parts obtained in the above examples and comparative examples were evaluated as follows.
[Ionic conductivity]
A coin-type cell was produced using the electronic component separators obtained in Examples 1 to 12 and Comparative Examples 1 to 3, and the ionic conductivity was measured. The results are shown in Table 1. The measurement environment and measurement apparatus are as follows.
Measurement environment: 20 ° C, 50% RH
Measuring device: Solartron's SI 1287 1255B

  As is apparent from Table 1, it was confirmed that the separators for electronic parts of Examples 1 to 12 of the present invention were superior in ion conductivity to Comparative Example 3. It is considered that this is because the low air permeability and the contact between the electrode and the separator with the resin layer on the separator surface without any gap are the factors that improve the ion conductivity.

[Shutdown]
Coin-type cells were produced using the electronic component separators obtained in Examples 1 to 3, 6 to 8, and 11 and Comparative Examples 2 and 3, and their shutdown properties were confirmed. The results are shown in Table 2. As a test method, the fully charged coin cell was further charged, the temperature change inside the battery at that time was measured, and the point at which the temperature began to fall was defined as the shutdown temperature.

  As is clear from Table 2, it was confirmed that the separator for electronic parts of the example of the present invention had a shutdown function. On the other hand, in Comparative Example 2, since the average particle diameter of the filler particles was constant, even when the filler particles were melted, the gap between the filler particles could not be filled and the battery reaction could not be suppressed, and the shutdown function did not work. When filler groups having different average particle diameters of the present invention were used, it was revealed that they have good shutdown properties. From this comparison, it can be seen that in the present invention, the voids between the filler particles are small, and therefore it is easy to provide a shutdown function.

[Short-circuiting]
A separator for electronic parts obtained in Examples 1 to 12 and Comparative Examples 1 to 3 cut into a 10 cm × 10 cm square is placed on a stainless steel flat plate, and a stainless steel cylinder with a bottom area of 0.5 cm ² is also used. An electrical short circuit between the stainless steel plate and the stainless steel cylinder was confirmed when pressed with a force of 30 kg using a shaped indenter. The results are shown in Table 3. ◯ indicates that no short circuit occurred, and x indicates that a short circuit occurred.

  None of the electronic component separators of the examples of the present invention were short-circuited. On the other hand, it was confirmed that the separators for electronic parts of Comparative Example 1 and Comparative Example 2 had a problem due to a short circuit. In particular, it was confirmed that the problem of the present invention was solved without causing a short circuit even with a thin separator having a thickness of 15 μm or less as in Examples 2, 5, 10, 11 and 12.

〔Heat-resistant〕
Regarding the separators for electronic parts of Examples 3, 5, 9, 10 and 12, the dimensional stability was confirmed. As a result, almost no dimensional change was observed even after standing for 10 hours in an atmosphere of 200 ° C. Since no change in air permeability was confirmed, it was confirmed that the heat resistance was good.

It is a figure explaining the relationship of the average particle diameter of two types of filler particles. It is the figure which showed an example of the microporous resin film. It is typical sectional drawing of the separator for electronic components which piled up two microporous resin films.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Microporous resin film 2 Through-hole 3 Porous structure A Filler particle B Filler particle

Claims (12)

  A separator for an electronic component containing at least two kinds of filler particles having different porous structures and average particle sizes, wherein the average particle sizes of the filler particles are a, b, c,. In this case, the relationship between adjacent average particle sizes is b ≧ {(2√3-3) / 3} a, c ≧ {(2√3-3) / 3} b,... N ≧ {( 2√3-3) / 3} m. The electronic component separator.   2. The electronic component separator according to claim 1, wherein at least one melting point of the filler particles is 80 ° C. or more.   The separator for electronic components according to claim 1, comprising a sheet-like porous substrate.   The sheet-like porous substrate is a non-woven fabric or has a through hole with an average pore diameter of 0.01 to 50 μm that does not substantially have a shielding structure penetrating in the direction perpendicular to the film surface, and is the shortest distance between adjacent through holes The separator for electronic parts according to claim 3, which is a microporous resin film having an average of 0.01 to 100 μm.   The separator for electronic parts according to claim 3, wherein the melting point of the sheet-like porous substrate exceeds 180 ° C.   The porous structure is a solvent-soluble resin, and the sheet-like porous base material and the filler particles do not substantially swell in the range up to 70 ° C. with respect to the organic electrolyte. The separator for electronic components as described in 2.   A step of placing a sheet-like porous substrate on one surface of the resin film, a resin that forms a porous structure on the sheet-like porous substrate, and at least a good solvent or a good solvent that dissolves the resin; A step of applying a coating solution containing both of the poor solvent, and drying the formed coating layer to remove the solvent, thereby forming a porous structure on the surface and / or inside of the sheet-like porous substrate. A step of obtaining a laminate, and then a step of peeling a resin film from the laminate, the sheet-like porous substrate and / or the coating liquid containing at least two kinds of filler particles having different average particle diameters When the average particle size of the filler particles is a, b, c,..., M, n in order of increasing size, the relationship between the adjacent average particle sizes is b ≧ {(2√3-3) / 3} a, c ≧ {(2√3-3) / 3} b,... N ≧ {(2√3-3) / 3} method for manufacturing an electronic component separator, which is a m.   The step of applying a coating liquid containing a resin that forms a porous structure and at least a good solvent that dissolves the resin or both a good solvent and a poor solvent on one surface of the resin film, the sheet-like porous substrate A step of superimposing on the coating layer obtained in the step, and then a step of obtaining a laminate in which a porous structure is formed on the surface and / or inside of the sheet-like porous substrate by drying and removing the solvent, Thereafter, there is a step of peeling the resin film from the laminate, and the filler has an average particle diameter of at least two kinds of filler particles having different average particle diameters in the sheet-like porous substrate and / or the coating liquid. Where a, b, c,..., M, n are the largest, the relationship between adjacent average particle sizes is b ≧ {(2√3-3) / 3} a, c ≧ {(2√3 -3) / 3} b, ... n ≧ {(2√3-3) / 3} Method for manufacturing an electronic component separator, characterized in that it.   A step of removing excess coating liquid after impregnating the sheet-like porous substrate into a coating liquid containing a resin that forms a porous structure and at least a good solvent that dissolves the resin or both a good solvent and a poor solvent; Thereafter, the solvent is removed by drying, or the liquid is substituted with the good solvent and the poor solvent by drying after being immersed in a liquid that replaces the good solvent and the poor solvent to remove the good solvent and the poor solvent. A, b, in order of increasing average particle diameter of the filler particles, including at least two or more kinds of filler particles having different average particle diameters in the sheet-like porous substrate and / or the coating liquid. When c,..., m, n, the relationship between adjacent average particle sizes is b ≧ {(2√3-3) / 3} a, c ≧ {(2√3-3) / 3} b. , ... n ≧ {(2√3-3) / 3} m Method of manufacturing goods for the separator.   The method for producing a separator for an electronic component according to any one of claims 7 to 9, wherein the amount of water contained in the coating liquid is 0.7% by weight or less as measured by a Karl Fischer method.   The method for manufacturing a separator for electronic parts according to any one of claims 7 to 9, wherein the boiling point of the poor solvent contained in the coating solution is higher than the boiling point of the good solvent.   The method for producing a separator for electronic parts according to claim 7 or 8, wherein the strength for peeling the resin film from the laminate is 0.1 to 75 g / 20 mm.

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