Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B29/00—Layered products comprising a layer of paper or cardboard
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/247—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using fibres of at least two types
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
  • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
  • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
  • D21H13/02—Synthetic cellulose fibres
  • D21H13/08—Synthetic cellulose fibres from regenerated cellulose
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/52—Separators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/004—Details
  • H01G9/02—Diaphragms; Separators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/443—Particulate material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
  • H01M50/491—Porosity
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/13—Energy storage using capacitors

Definitions

• the present invention relates to a thin-film sheet having a fine network structure made of fine cellulose fibers, a core material for fiber-reinforced plastic film using the same, a core material for printed wiring boards for electronic materials, a core material for insulating films, and a core material
• the present invention relates to a core material, an electricity storage device separator, and the like.
• Fiber reinforced plastic FRP: Fiber Reinforced Plastics
• FRP Fiber Reinforced Plastics
• Fiber reinforced composite materials consisting of glass fibers, carbon fibers, aramid fibers, etc. and matrix resins are lightweight compared to competing metals, etc., but have excellent mechanical properties such as strength and elastic modulus. It is used in many fields such as spacecraft members, automobile members, ship members, civil engineering and building materials, and sports equipment. Particularly in applications where high performance is required, carbon fibers excellent in specific strength and specific elastic modulus are often used as reinforcing fibers.
• thermosetting resins such as unsaturated polyester resins, vinyl ester resins, epoxy resins, phenol resins, cyanate ester resins, and bismaleimide resins are often used as matrix resins, with excellent adhesion to carbon fibers.
• epoxy resins are used.
• a vacuum impregnation molding method (VaTM Vaum assist Resin Transfer Molding) has been adopted. (For example, see the following Patent Document 1).
• VaTM Vaum assist Resin Transfer Molding has been adopted.
• These technologies are suitable for improving the heat resistance and strength of resins. For example, along with the recent trend toward higher functionality in the electronic equipment field, electronic materials have become smaller and thinner (thickness on the order of several tens of microns).
• this fine cellulose sheet having a number average fiber diameter of 200 nm or less has high porosity, it has been found that the resin impregnation property is low because each pore diameter is too small. Therefore, it is unsuitable for compounding with a resin, and a technique for stably producing a sheet having a low thermal expansion property and heat resistance required for a substrate in the field and having a film thickness of 25 ⁇ m or less is not necessarily required. The current situation was not established.
• power storage devices mainly include battery-type devices such as nickel / hydrogen batteries and lithium secondary ion batteries, and capacitor-type devices such as aluminum electrolytic capacitors and electric double layer capacitors.
• capacitor-type devices such as aluminum electrolytic capacitors and electric double layer capacitors.
• the capacitance of a capacitor-based device has been a relatively small capacitance on the order of several pF (picofarad) to several mF (millifarad), but in recent years, a large-capacitance type capacitor such as an electric double layer capacitor has been used. It has emerged and is reaching a level comparable to battery-based devices in terms of energy density.
• high-capacity capacitors do not have a conventional battery that (1) excels in repeated resistance because it does not involve an electrochemical reaction, and (2) it has a high output density and can output stored electricity all at once. Taking advantage of the unique characteristics of the capacitor, it is attracting attention as an onboard storage device for next-generation vehicles such as hybrid vehicles and fuel cell vehicles.
• the separator which is one of the main members in many electricity storage devices
• the required performance varies naturally depending on the type of electricity storage device.
• short circuit resistance long-term performance maintenance in the device usage environment (for example, high temperature under charging environment, long-term stability), (2) limited space Among these, there is a required performance of achieving a high capacity without increasing the volume, or forming a power storage device with a high volumetric energy density (or light weight and miniaturization with the same performance).
• the separator is essentially made of a heat resistant material, ( In order to solve the problem 2), it is necessary to be overwhelmingly thinner than the conventional separator film. In order to solve these problems, many inventions have been made with respect to a cellulose-based separator having excellent surface characteristics in terms of impregnation with respect to many electrolytic solutions.
• Patent Document 4 reports a technique in which a separator using a beating raw material of solvent-spun cellulose fiber that can be beaten as a raw material in a range of 60 to 100% by weight is used in an electric double layer capacitor. Since the beating raw material of solvent-spun cellulose fiber that can be beaten is used as the raw material for the separator, the fibrils obtained by beating give the separator a very dense structure and high density to improve the short-circuit defect rate. In order to improve internal resistance, it is disclosed that a separator maintaining a through hole as a path through which ions pass can be obtained. On the other hand, since thick fibers remain, the thickness of the separator obtained is only an example up to 25 ⁇ m, and it is stated that further thinning is difficult, and does not satisfy the high efficiency of power storage. .
• Patent Documents 2 and 3 report a separator for an electricity storage device using cellulose fibers having a maximum fiber diameter of 1,000 nm or less and a crystallinity obtained by a solid NMR method of 60% or more. Has been. These technologies form a separator for an electricity storage device using fine cellulose having a number average fiber diameter of 200 nm or less from the viewpoint of easily creating a microporous structure. Although it is a technology that expresses low internal resistance by making the cellulose fiber diameter very small and forming a microporous structure, in the electricity storage device using this separator, the fibers are too thin and the surface area is large.
• JP 60-83826 A Japanese Patent No. 4628764 International Publication No. 2006/004012 Pamphlet JP 2000-3834 A
• the film is a thin film and has thermal stability (linear thermal expansion coefficient and elastic retention at high temperature) required for an insulating film for electronic materials, etc.
• thermal stability linear thermal expansion coefficient and elastic retention at high temperature
• the present invention is a microporous and high-porosity fine cellulose sheet made of fine cellulose fibers, which corresponds to the specific surface area of regenerated cellulose fine fibers.
• a thin film sheet material that can solve the above-mentioned problems by designing the fiber diameter to be 0.20 ⁇ m to 2.0 ⁇ m, the air resistance is 1 s / 100 ml to 100,000 s / 100 ml, and the film thickness is 2 ⁇ m to 22 ⁇ m. As a result, the present invention has been completed.
• the present invention is as follows: [1] A thin film sheet composed of a single layer containing at least one cellulose fine fiber layer containing 50% by weight or more of regenerated cellulose fine fibers or a plurality of layers of 3 layers or less, and the following requirements: (1) The specific surface area equivalent fiber diameter of the fibers constituting the cellulose fine fiber layer is 0.20 ⁇ m or more and 2.0 ⁇ m or less; (2) Air permeability resistance is 1 s / 100 ml or more and 100,000 s / 100 ml or less; and (3) Film thickness is 2 ⁇ m or more and 22 ⁇ m or less; A thin film sheet characterized by satisfying [2] The thin film sheet according to [1], containing 60% by weight or more of the regenerated cellulose fine fiber.
• a multi-layer structure of more than the three layers having a basis weight including the base layer is a nonwoven fabric or paper is 3 g / m 2 or more 20 g / m 2 or less, any one of [1] to [12]
• one layer of the multilayer structure of more than the three layers having a basis weight including the base layer is a nonwoven fabric or paper is 15 g / m 2 or less 3 g / m 2 or more, the thin film sheet according to [13].
• the composite sheet according to [20], wherein the inorganic fine particles are one or more selected from the group consisting of SiO 2 , TiO 2 , Al 2 O 3 , ZrO 2 , MgO, ZnO, and BaTiO 3 .
• a composite prepreg sheet comprising the thin film sheet according to any one of (A) [1] to [14] and (B) a thermosetting resin and / or a photocurable resin.
• the composite prepreg sheet according to [22], wherein the (B) resin is an epoxy resin or an acrylic resin.
• a fiber reinforced plastic sheet core material comprising the thin film sheet according to any one of [1] to [14].
• the fiber-reinforced plastic sheet core material according to [26] which is a core material for a printed wiring board for electronic materials.
• a prepreg for a fiber-reinforced plastic sheet comprising the thin film sheet according to any one of [1] to [14].
• the fiber-reinforced plastic sheet according to [34] which is a printed wiring board for electronic materials.
• the fiber-reinforced plastic sheet according to [34] which is an insulating film for electronic materials.
• An electricity storage device separator comprising the thin film sheet according to any one of [1] to [14] or the laminated thin film sheet according to [38] or [39].
• the electricity storage device separator according to [40] wherein the electricity storage device is an electric double layer capacitor.
• the thin film sheet of the present invention is thin and excellent in uniformity, and has a limited air permeability resistance range, that is, a pore diameter. Therefore, for example, when used as a core material for fiber reinforced plastic, thermal stability (reduction of linear thermal expansion coefficient and elastic retention at high temperature) at the time of compounding with resin can be imparted. Moreover, when it uses as a core material for printed wiring boards for electronic materials, a core material for insulating films, and a core material for core materials, it is possible to ensure both sheet strength and thermal stability in a thin film. Furthermore, when used as a separator for an electricity storage device, it is a thin film and has excellent short-circuit resistance, heat resistance, and chemical / physical stability. Internal resistance, small leakage current value, etc.) and long-term stability can be realized.
• cellulose nanofibers having a predetermined range of fiber diameters can be provided by miniaturization.
• the thin film sheet thus produced is thin and excellent in uniformity, and has a limited air permeability resistance range, that is, a pore diameter. Therefore, for example, when used as a core material for fiber-reinforced plastics, thermal stability (reduction in the coefficient of linear thermal expansion and retention of elastic modulus) can be imparted when combined with a resin.
• an insulating film core material when used as a core material for printed wiring boards, an insulating film core material, and a core material core material for electronic materials, it is possible to achieve both insulation and thermal stability in a thin film. Furthermore, when used as a separator for an electricity storage device, it is a thin film and has excellent short-circuit resistance, heat resistance, and chemical / physical stability. Internal resistance, small leakage current, etc.) and long-term stability can be achieved.
• the thin film sheet of the present embodiment is a thin film sheet composed of a single layer including at least one cellulose fine fiber layer containing 50% by weight or more of regenerated cellulose fine fibers or a plurality of layers of three or less layers, and the following requirements: (1) The specific surface area equivalent fiber diameter of the fibers constituting the cellulose fine fiber layer is 0.20 ⁇ m or more and 2.0 ⁇ m or less; (2) Air permeability resistance is 1 s / 100 ml or more and 100,000 s / 100 ml or less; and (3) Film thickness is 2 ⁇ m or more and 22 ⁇ m or less; Is a thin film sheet characterized by satisfying Such a thin film sheet can be suitably used as a thin film core material for fiber reinforced plastic films, a core material for printed wiring boards for electronic materials, a core material for insulating films, a core material for core materials, and a separator for electricity storage devices. The reason will be described below.
• a nonwoven fabric separator and a microporous membrane (generally a porous membrane) separator can be considered as in the present invention. It has been found that cellulosic nonwoven fabrics are particularly desirable when assuming similar porosity. The reason why cellulose is desirable as a material is that it has amphiphilic surface characteristics (for example, H. Ono et al., Trans. Mat. Res. Soc. Jpn., 26, 569-572 (2001)) It is because the wettability with respect to the water-system electrolyte solution or organic-system electrolyte solution used with many electrical storage devices is very favorable.
• cellulose nonwoven fabric paper
• the reason why the nonwoven fabric film is superior to the microporous film is that the former is a closed pore (one side of the hole is connected to the through hole) in addition to the open pore (the hole having the through hole or both sides of the hole leading to the through hole)
• the structure consists of almost only open pores, and when the surface wettability is good, it is possible to create a state where most of the pores are occupied by the electrolyte. is there.
• a gas phase such as air has a higher resistance value than the electrolytic solution, so the presence of closed pores inhibits the reduction of internal resistance.
• Further measures to reduce the internal resistance are to reduce the thickness of the separator, but there is a limit to reducing the thickness of the non-woven fabric with normal fibers (thin fibers having a fiber diameter of several ⁇ m or more). is there. This is because if the separator is made of a relatively thick fiber and is thin and has a high porosity, the diameter of the through-hole becomes large, causing a problem in short-circuit resistance. In other words, to provide a thin non-woven membrane that contributes to a reduction in internal resistance with a high porosity and a small through-hole diameter, it is essential to use cellulose fibers having a fine fiber diameter.
• the regenerated cellulose is a substance obtained by regenerating natural cellulose by dissolving or crystal swelling (mercelization) treatment, and the lattice spacing of 0.73 nm, 0.44 nm and 0.
• a ⁇ -1,4-linked glucan (glucose polymer) having a molecular arrangement that gives a crystal diffraction pattern (cellulose type II crystal) with a diffraction angle corresponding to 40 nm as the apex.
• an X-ray diffraction pattern in which the range of 2 ⁇ ranges from 0 ° to 30 ° includes one peak at 10 ° ⁇ 2 ⁇ ⁇ 19 °, and two peaks at 19 ° ⁇ 2 ⁇ ⁇ 30 °.
• the maximum fiber thickness of the regenerated cellulose fine fiber is preferably 15 ⁇ m or less. More preferably, it is 10 micrometers or less, More preferably, it is 5 micrometers or less, Most preferably, it is 3 micrometers or less.
• the maximum fiber thickness of 15 ⁇ m or less means that no fibers exceeding a fiber diameter of 15 ⁇ m can be confirmed on the image in an electron microscope (SEM) of a cellulose nonwoven fabric measured under the following conditions. .
• SEM electron microscope
• the maximum fiber diameter is defined as 15 ⁇ m or less. However, if it can be clearly confirmed that several fine fibers are bundled in the image to have a fiber diameter of 15 ⁇ m or more, it is not considered as a fiber having a fiber diameter of 15 ⁇ m or more. If the maximum fiber thickness exceeds 15 ⁇ m, the thickness of the sheet will increase, so that it is difficult to ensure uniformity of the hole diameter and the like in the production of thin fiber reinforced plastics, electronic insulation films, and separators. Absent.
• the fiber diameter corresponding to the specific surface area of the cellulose fine fiber layer containing 50% by weight or more of regenerated cellulose is preferably 2.0 ⁇ m or less, more preferably 1.0 ⁇ m or less, and further preferably 0.45 ⁇ m or less. Most preferably, it is 0.40 ⁇ m or less.
• the specific surface area equivalent fiber diameter will be described.
• the specific surface area is first evaluated using the BET method by nitrogen adsorption, and the fibers constituting the separator are virtually in an ideal state in which no fusion between the fibers occurs with respect to the specific surface area, and the cellulose density is By a cylindrical model assuming that the surface is constituted by fibers that are infinite cylinders with d (g / cm 3 ) and L / D (L: fiber length, D: fiber diameter (both units: ⁇ m)).
• the following formula for specific surface area and fiber diameter: Specific surface area 4 / (dD) (m 2 / g) Induced.
• the specific surface area measurement by the BET method is performed by measuring the adsorption amount of nitrogen gas at the boiling point of liquid nitrogen with respect to about 0.2 g of sample with a specific surface area / pore distribution measuring device (manufactured by Beckman Coulter). Then, the specific surface area was calculated.
• the thin film sheet of this embodiment suitably provides a thin film sheet having a uniform thickness distribution by selecting the fiber diameter corresponding to the specific surface area of the cellulose fine fiber layer containing 50% by weight or more of regenerated cellulose fine fibers within the above range. be able to.
• the fiber diameter corresponding to the specific surface area of the cellulose fine fiber layer containing 50% by weight or more of the regenerated cellulose exceeds 2.0 ⁇ m, the fiber diameter is too thick, so that the unevenness on the surface of the fine fiber sheet is generated and the microporous structure is distributed. Becomes large, that is, because holes having large pore diameters are scattered, it becomes impossible to provide a thin and excellent sheet.
• the thin film sheet of this embodiment is used as a separator, if the fiber diameter corresponding to the specific surface area of the cellulose fine fiber layer is more than 2.0 ⁇ m, it is pursued to reduce the thickness while maintaining short-circuit resistance. This is not preferable because it does not meet one of the objects of the invention.
• the specific surface area equivalent fiber diameter of the cellulose fine fiber layer containing 50% by weight or more of regenerated cellulose fine fibers as the thin film sheet of this embodiment is preferably 0.20 ⁇ m or more, and more preferably 0.25 ⁇ m or more.
• the fiber diameter corresponding to the specific surface area of the cellulose fine fiber layer containing 50% by weight or more of regenerated cellulose is less than 0.20 ⁇ m, the pore diameter of the fine fiber sheet becomes too small. Therefore, the resin is not impregnated when compounding the thin film sheet and resin for fiber reinforced plastics, and when the long-term stability evaluation is continued by charging / discharging the storage device, the fiber diameter is too thin, causing deterioration. Cause an increase in internal resistance with time and gas generation.
• the regenerated cellulose fine fiber is contained by 50% by weight or more as the thin film sheet of the present embodiment. More preferably, it is 60 wt%, more preferably 70 wt% or more, and most preferably 80 wt% or more.
• fine fibers containing 50% by weight or more of regenerated cellulose it is possible to suppress the shrinkage of the fine fiber layer during drying when forming a sheet by a papermaking method or a coating method using cellulose nanofiber slurry in water. It becomes possible to maintain the pores and hole diameter in the fiber layer.
• the resin when a thin film sheet and a resin are combined in a fiber reinforced plastic application, the resin is easily impregnated and easily combined, and the number of entanglement points of the regenerated cellulose fine fiber is larger than that of a normal cellulose fiber sheet.
• the thermal stability reduction of the coefficient of linear thermal expansion, elasticity retention at high temperature
• the thin film sheet of this embodiment is characterized in that the air permeability resistance is in the range of 1 s / 100 cc to 100,000 s / 100 cc.
• the air resistance means a numerical value measured based on the Gurley tester method described in JIS P8117. More preferably, the air resistance is 2 s / 100 cc to 10,000 s / 100 cc, more preferably 5 s / 100 cc to 1,000 s / 100 cc, and most preferably 8 s / 100 cc to 40 s / 100 cc. is there.
• a sheet having an air permeability resistance lower than 1 s / 100 cc it is difficult to produce the sheet uniformly without defects even though it is composed of fine fibers.
• the film thickness is substantially 2 ⁇ m or more and 22 ⁇ m or less due to processing and functional limitations.
• the film thickness is measured by using a surface contact type film thickness meter, such as a Mitutoyo film thickness meter (Model ID-C112XB) or the like, and cutting a 10.0 cm ⁇ 10.0 cm square piece from the separator.
• the average value of the five measured values for the position is defined as film thickness T ( ⁇ m).
• the thin film sheet of this embodiment has a thickness of 5 ⁇ m to 21 ⁇ m, and more preferably 8 ⁇ m to 19 ⁇ m.
• the film thickness is in the above range, the thickness can be minimized when a composite sheet is produced as an electronic material insulating film.
• the separator has extremely good electrical characteristics (functional aspects) such as low internal resistance and handling properties when winding the separator to assemble a device. Even when the thin film sheet of the present invention is used for a fiber reinforced plastic, if the film thickness is within this range, it is effective in terms of weight reduction and compactness.
• the thickness is less than 2 ⁇ m, handling may be difficult in the device assembling process, which may be inappropriate, and this is not preferable from the viewpoint of long-term stability of short-circuiting due to deterioration over time.
• the thickness is larger than 22 ⁇ m, a desirable effect such as a reduction in internal resistance may not be expected.
• the basis weight of the cellulose fine fiber layer used in the thin film sheet of the present embodiment is 1 g / m 2 or more and 20 g / m 2 or less, more preferably 3 g / m 2 or more and 15 g / m 2 or less, and further preferably 4 g / m 2 or more. 13 g / m 2 or less. If the basis weight is less than 1 g / m 2 , it may be difficult to handle in the assembly process to various devices and may be inappropriate, which is not preferable from the viewpoint of long-term stability.
• the basis weight is larger than 20 g / m 2 , the film cannot be thinned, and the pore diameter and porosity in the thin film sheet are reduced, the resin impregnation property is deteriorated, and the separator basis weight is increased as a separator. There is a possibility that desired effects such as low internal resistance cannot be expected.
• the cellulose fine fiber layer containing 50% by weight or more of regenerated cellulose fine fibers used in the thin film sheet of this embodiment may further contain natural cellulose fine fibers in an amount of less than 50% by weight in addition to the regenerated cellulose fine fibers. .
• natural cellulose fine fibers By using natural cellulose fine fibers, it is relatively easy to produce fine cellulose fibers having a fiber diameter of less than 0.20 ⁇ m from the fineness of microfibrils, which are the structural units, and the finer fiber length / fiber
• the content is more preferably less than 40% by weight, still more preferably 30% by weight.
• the maximum fiber thickness is preferably 15 ⁇ m or less. If the maximum fiber diameter is too large, it may not be suitable for one of the purposes of the present invention to pursue thinning by utilizing high uniformity based on the microporous structure by the fine fibers described above, and may not be preferable.
• Natural cellulose fine fibers whose maximum fiber diameter does not exceed 15 ⁇ m include wood pulp obtained from hardwoods or conifers, refined linters, or refined pulps from various plant species (bamboo, hemp fiber, bagasse, kenaf, linter, etc.) In addition to those obtained by highly refining and the like, natural cellulose fine fibers that are aggregates of never-dry and fine fibers such as bacterial cellulose (BC) produced by cellulose-producing bacteria (bacteria) are also included.
• BC bacterial cellulose
• bacteria cellulose-producing bacteria
• the cellulose fine fiber layer containing 50% by weight or more of regenerated cellulose fine fibers used in the thin film sheet of this embodiment 50% by weight of fine fibers made of an organic polymer other than cellulose in addition to the regenerated cellulose fine fibers. Less than 40% by weight, more preferably less than 30% by weight.
• the organic polymer any organic polymer capable of producing fine fibers can be used.
• aromatic or aliphatic polyester, nylon, polyacrylonitrile, cellulose acetate, polyurethane, polyethylene, polypropylene, polyketone, Natural organic polymers other than cellulose, such as aromatic polyamide, polyimide, silk, and wool, can be mentioned, but are not limited thereto.
• the fine fibers made of the organic polymer are fine fibers obtained by beating organic fibers, finely fibrillated or miniaturized by a high-pressure homogenizer, etc., fine fibers obtained by electrospinning using various polymers as raw materials, and various polymers.
• examples thereof include, but are not limited to, fine fibers obtained by the melt blown method.
• a microfibrous aramid obtained by refining an aramid fiber, which is a polyacrylonitrile nanofiber or wholly aromatic polyamide, with a high-pressure homogenizer is particularly suitable for use due to the high heat resistance and high chemical stability of the aramid fiber. be able to.
• the maximum fiber thickness is preferably 15 ⁇ m or less. If the maximum fiber diameter is too large, it may not be suitable for one of the purposes of the present invention to pursue thinning by utilizing high uniformity based on the microporous structure by the fine fibers described above, and may not be preferable.
• the refining of the cellulose fiber is preferably performed through a pretreatment step, a beating treatment step, and a refining step for both the regenerated cellulose fiber and the natural cellulose fiber.
• the pretreatment step can be carried out in a water washing step using a surfactant to remove the oil agent, and in the pretreatment step of natural cellulose fiber, It is effective to make the raw material pulp easy to be refined in the subsequent steps by autoclave treatment under an impregnation in water at a temperature of 150 ° C., enzyme treatment, or a combination thereof.
• an inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, etc.) or an organic acid (acetic acid, citric acid, etc.) having a concentration of 1% by weight or less may be added for autoclaving.
• These pretreatments not only reduce the load of the micronization process, but also discharge impurity components such as lignin and hemicellulose present on the surface and gaps of the microfibrils that make up the cellulose fibers to the aqueous phase, resulting in a finer process. Since there is an effect of increasing the ⁇ -cellulose purity of the formed fiber, it may be very effective for improving the heat resistance of the fine cellulose fiber nonwoven fabric.
• both regenerated cellulose fiber and natural cellulose fiber are produced with the following contents.
• the raw material pulp is 0.5 wt% or more and 4 wt% or less, preferably 0.8 wt% or more and 3 wt% or less, more preferably 1.0 wt% or more and 2.5 wt% or less.
• a beating device such as a beater or disc refiner (double disc refiner).
• a disc refiner When a disc refiner is used, if the clearance between the discs is set as narrow as possible (for example, 0.1 mm or less) and processing is performed, extremely advanced beating (fibrillation) proceeds, so a high-pressure homogenizer or the like is used.
• the conditions for the miniaturization treatment can be relaxed and may be effective.
• the solid content concentration in the aqueous dispersion is 0.5 wt% or more and 4 wt% or less, preferably 0.8 wt% or more and 3 wt% or less, more preferably 1.0 wt. % By weight to 2.5% by weight. In the case of a solid content concentration in this range, clogging does not occur and an efficient miniaturization process can be achieved.
• high-pressure homogenizer examples include NS type high-pressure homogenizer manufactured by Niro Soabi (Italy), SMT Co., Ltd., Lanier type (R model) pressure-type homogenizer, Sanwa Kikai Co., Ltd. high-pressure type homogenizer, and the like. Any device other than these devices may be used as long as the device performs miniaturization by a mechanism substantially similar to those of these devices.
• Ultra-high pressure homogenizers mean high-pressure collision type miniaturization machines such as Mizuho Kogyo Co., Ltd. microfluidizer, Yoshida Kikai Kogyo Co., Ltd. Nanomizer, Sugino Machine Ultimate Co., Ltd.
• any device other than these devices may be used as long as the device performs miniaturization with a substantially similar mechanism.
• the grinder-type miniaturization device include the pure fine mill of Kurita Machinery Co., Ltd. and the stone mill type milling die represented by Masuyuki Sangyo Co., Ltd. Any device other than these may be used as long as the device performs miniaturization by this mechanism.
• the fiber diameter of the fine cellulose fiber is determined according to the conditions for refinement using a high-pressure homogenizer (selection of equipment and operating pressure and number of passes) or pre-treatment conditions (for example, autoclave treatment, enzyme treatment, beating treatment). Etc.). Furthermore, as the natural cellulose fine fiber, the cellulose fine fiber to which the chemical treatment of the surface is added, and the cellulose type in which the hydroxyl group at the 6-position is oxidized by the TEMPO oxidation catalyst to become a carboxyl group (including acid type and salt type). It is also possible to use fine fibers.
• hydroxyl groups present on the surface of the fine cellulose fiber are esterified including acetate ester, nitrate ester, sulfate ester.
• etherified products including alkyl ethers typified by methyl ether, carboxy ethers typified by carboxymethyl ether, and cyanoethyl ether can be appropriately prepared and used.
• a high-energy refining device such as a high-pressure homogenizer.
• a dispersion can be obtained.
• 2,2,6,6-tetramethylpiperidinooxy is added to an aqueous dispersion of natural cellulose.
• TEMPO a catalyst called TEMPO such as a radical
• an oxidant such as hypochlorous acid
• the above-mentioned regenerated cellulose or natural cellulose fine fibers with different raw materials, natural cellulose fine fibers with different degrees of fibrillation, natural cellulose fine fibers whose surfaces are chemically treated, organic polymer fine fibers It may be effective to form a cellulose fine fiber layer by mixing a predetermined amount of two or more of the above.
• the cellulose fine fiber layer used for the thin film sheet of this embodiment contains 10 weight% or less of a reactive crosslinking agent, it may be effective for strength reinforcement.
• the reactive crosslinking agent refers to a reactant derived from a polyfunctional isocyanate, and refers to a resin produced by an addition reaction between a polyfunctional isocyanate compound and an active hydrogen-containing compound.
• polyfunctional isocyanate compound that forms the reactive crosslinking agent in the cellulose fine fiber layer used in the thin film sheet of the present embodiment
• aromatic polyfunctional isocyanate, araliphatic polyfunctionality Examples include isocyanates, alicyclic polyfunctional isocyanates, and aliphatic polyfunctional isocyanates. From the viewpoint of low yellowing, alicyclic polyfunctional isocyanates and aliphatic polyfunctional isocyanates are more preferable.
• the polyfunctional isocyanate compound may be contained 1 type, or 2 or more types.
• aromatic polyfunctional isocyanate examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and a mixture thereof (TDI), diphenylmethane-4,4′-diisocyanate (MDI), naphthalene-1,5.
• -Aromatic polyfunctional isocyanates such as diisocyanate, 3,3-dimethyl-4,4-biphenylene diisocyanate, crude TDI, polymethylene polyphenyl diisocyanate, crude MDI, phenylene diisocyanate, xylylene diisocyanate;
• alicyclic polyfunctional isocyanate include alicyclic polyfunctional isocyanates such as 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, and cyclohexane diisocyanate.
• Examples of the aliphatic polyfunctional isocyanate include aliphatic polyfunctional isocyanates such as trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate, pentamethylene diisocyanate, and hexamethylene diisocyanate.
• Examples of the active hydrogen-containing compound include a hydroxyl group-containing compound including a monohydric alcohol, a polyhydric alcohol, and phenols, an amino group-containing compound, a thiol group-containing compound, and a carboxyl group-containing compound. Also included are water and carbon dioxide present in the air or in the reaction field. One kind or two or more kinds of active hydrogen-containing compounds may be contained.
• monohydric alcohols examples include alkanols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), and alkenols having 2 to 20 carbon atoms (oleyl alcohol). And linoleyl alcohol) and araliphatic alcohols having 7 to 20 carbon atoms (such as benzyl alcohol and naphthylethanol).
• polyhydric alcohols examples include dihydric alcohols having 2 to 20 carbon atoms [aliphatic diols (ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol).
• 1,10-decanediol, etc. 1,10-decanediol, etc.
• alicyclic diols cyclohexanediol, cyclohexanedimethanol, etc.
• araliphatic diols ⁇ 1,4-bis (hydroxyethyl) benzene etc. ⁇ , etc.
• carbon number 3-20 Trihydric alcohols [aliphatic triols (such as glycerin and trimethylolpropane)] and 4- to 8-hydric alcohols having 5 to 20 carbon atoms [aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin and dipentaerythritol) Etc.) and sugars (sucrose, guru) Over scan, mannose, fructose, methyl glucoside and derivatives thereof)], and the like.
• phenols examples include monohydric phenols (phenol, 1-hydroxynaphthalene, anthrol, 1-hydroxypyrene, etc.), polyhydric phenols (phloroglucin, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, 1,4,5,8-tetrahydroxyanthracene, condensate of phenol and formaldehyde (novolak), polyphenol described in US Pat. No. 3,265,641], etc. It is done.
• amino group-containing compound examples include monohydrocarbylamines having 1 to 20 carbon atoms [alkylamine (butylamine and the like), benzylamine and aniline and the like], aliphatic polyamines having 2 to 20 carbon atoms (ethylenediamine, hexamethylenediamine and the like).
• Diethylenetriamine, etc. Diethylenetriamine, etc.), C6-C20 alicyclic polyamines (diaminocyclohexane, dicyclohexylmethanediamine, isophoronediamine, etc.), C2-C20 aromatic polyamines (phenylenediamine, tolylenediamine, diphenylmethanediamine, etc.), carbon Heterocyclic polyamines of 2 to 20 (such as piperazine and N-aminoethylpiperazine), alkanolamines (such as monoethanolamine, diethanolamine and triethanolamine), dicarboxylic acid and excess poly Polyamide polyamine, polyether polyamine, hydrazine (hydrazine and monoalkylhydrazine etc.), dihydrazide (eg succinic acid dihydrazide and terephthalic acid dihydrazide etc.), guanidine (butyl guanidine and 1-cyanoguanidine etc.), dicyandiamide, etc
• Examples of the thiol group-containing compound include monovalent thiol compounds having 1 to 20 carbon atoms (alkyl thiol such as ethyl thiol, phenyl thiol and benzyl thiol), and polyvalent thiol compounds (ethylene dithiol and 1,6-hexanedithiol). Etc.).
• Examples of the carboxyl group-containing compound include monovalent carboxylic acid compounds (alkyl carboxylic acids such as acetic acid, aromatic carboxylic acids such as benzoic acid), polyvalent carboxylic acid compounds (alkyl dicarboxylic acids such as oxalic acid and malonic acid, and terephthalic acid. Aromatic dicarboxylic acids such as acids) and the like.
• the cellulose fine fiber layer used in the thin film sheet of this embodiment has a basis weight of 3 g / m 2 or more and 20 g / m 2 or less, more preferably 15 g / m 2 or less as one layer of a multilayer structure of 3 layers or less.
• the base material layer which is paper may be included.
• a base material layer that is a nonwoven fabric or paper having a basis weight of 3 g / m 2 or more and 20 g / m 2 or less, even if the strength of the thin cellulose fine fiber layer itself is insufficient, the base material layer has the strength. In order to compensate, it becomes a thin film sheet that is extremely easy to handle when producing members and parts while maintaining the function as a thin film sheet.
• Examples of the base material layer used in the thin film sheet of the present embodiment include polyamide fibers such as 6-nylon and 6,6-nylon, polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate, polyethylene fibers, It is a nonwoven fabric or paper comprising at least one selected from the group consisting of polypropylene fibers, natural cellulose fibers such as wood pulp and cotton linter, regenerated cellulose fibers such as viscose rayon and copper ammonia rayon, and purified cellulose fibers such as lyocell and tencel. .
• the said base material layer can be conveniently used from the film thickness range prescribed
• an insulating porous film may be formed on one side or both sides.
• a thin film sheet is used as a separator for a power storage device, if the power storage device generates local heat inside the battery due to an internal short circuit or the like, the separator around the heat generation site contracts and the internal short circuit further expands. , Runaway fever may lead to serious events such as ignition and rupture.
• By providing a laminated structure in which an insulating porous film is formed on one side or both sides of a thin film sheet it is possible to prevent the occurrence or expansion of a short circuit and provide a highly safe power storage device.
• the insulating porous film formed on the one or both surfaces of the laminated thin film sheet of the present embodiment is composed of an inorganic filler and a thermosetting resin, and the void between the inorganic fillers without the thermosetting resin burying the inorganic filler. Is preferably maintained.
• the inorganic filler include calcium oxide, sodium carbonate, alumina, gibbsite, boehmite, magnesium oxide, magnesium hydroxide, silica, titanium oxide, barium titanate, zirconium oxide, and other inorganic oxides, inorganic hydroxides, and aluminum nitride.
• inorganic nitrides such as calcium nitride, calcium fluoride, barium fluoride, barium sulfate, silicon, aluminum compounds, zeolite, apatite, kaolin, mullite, spinel, olivine, mica, and montmorillonite .
• thermosetting resin used in the present embodiment examples include an epoxy resin, an acrylic resin, an oxetane resin, an unsaturated polyester resin, an alkyd resin, a novolac resin, a resole resin, a urea resin, and a melamine. System resin etc. are mentioned, These can also be used independently and can also use 2 or more types together.
• thermosetting resins are preferably water dispersions in terms of ease of handling and safety.
• the aqueous dispersion may contain a dispersant, an emulsifier, an organic solvent and the like as necessary.
• Examples of the epoxy resin include copolymers such as glycidyl acrylate, acrylic acid, methyl methacrylate, methacrylic acid, butyl methacrylate, and styrene.
• Examples of the acrylic resin include copolymers such as methyl methacrylate, butyl acrylate, methacrylic acid, hydroxyethyl methacrylate, and styrene.
• the insulating porous film formed on the thin film sheet of this embodiment on one side or both sides is prepared by bringing a mixed slurry of an inorganic filler and a thermosetting resin into contact with a non-woven fabric substrate and drying it. Stick. You may add a thickener, an antifoamer, and an organic solvent to a mixing slurry as needed.
• the insulating porous film on one side or both sides formed in the laminated thin film sheet of this embodiment preferably has a basis weight of 2 g / m 2 or more and 10 g / m 2 or less. If the basis weight is 2 g / m 2 , pinholes may be generated.
• the content of the inorganic filler in the laminated thin film sheet is preferably 15.0 to 50.0% by weight.
• the solid content of the thermosetting resin in the separator is more preferably 1.0 to 15.0% by weight. If the content of the inorganic filler is less than 10.0% by weight and the solid content of the thermosetting resin is more than 20.0% by weight, pinholes may be generated. If the content of the inorganic filler is more than 70.0% by weight and the solid content of the thermosetting resin is less than 0.1% by weight, the inorganic filler may fall off or peel off.
• the chlorine ion-containing concentration that is one measure of the amount of contained metal ions is preferably 40 ppm or less depending on the application.
• metal ions such as Na and Ca are also contained at a relatively low concentration.
• the heat resistance of the separator and the electricity of the electricity storage device incorporating the separator are included. This is because the inhibition of characteristics can be suppressed. More preferably, the heat resistance is more suitably developed when the content is 30 ppm or less, and most preferably 25 ppm or less.
• the chloride ion concentration can be evaluated by ion chromatography.
• a dispersion liquid in which regenerated cellulose fine fibers are highly dispersed in a dispersion medium such as water is formed into a film by a papermaking method or a coating method. From the viewpoint of the efficiency of the film forming method, it is preferable to form the film by a paper making method.
• a paper making method Conventionally, in order to produce a thin film sheet having a high porosity from cellulose fine fibers as in the present invention, in a wet paper formed by papermaking in order to suppress fusion and aggregation between fibers during drying.
• the regenerated cellulose fine fiber having a specific surface area equivalent diameter of 0.20 ⁇ m or more and 2.0 ⁇ m or less is a single-layer papermaking (weight per unit: 10 g / m 2 ) from an aqueous dispersion containing only the corresponding regenerated cellulose fine fiber. It means a regenerated cellulose fine fiber having a specific surface area equivalent fiber diameter of 0.20 ⁇ m or more and 2.0 ⁇ m or less calculated from the specific surface area measurement by the BET method of the single layer sheet obtained when the film is formed. To do.
• the fiber diameter corresponding to the specific surface area is preferably 0.25 ⁇ m or more.
• the fiber diameter corresponding to the specific surface area is preferably 1.0 ⁇ m or less, more preferably 0.45 ⁇ m or less, and most preferably 0.40 ⁇ m or less. If the fiber diameter corresponding to the specific surface area is smaller than 0.20 ⁇ m, it is difficult to maintain pores suitable for the thin film sheet of the present invention from drying from the aqueous wet paper, and the fiber diameter corresponding to the specific surface area is 2.0 ⁇ m. If it is larger than that, a problem that it becomes impossible to achieve both thin film thickness and uniformity tends to occur.
• a dispersion method for highly dispersing cellulose fine fibers as an aqueous dispersion for papermaking or coating is also important. It greatly affects the uniformity of thickness.
• the separator containing the regenerated cellulose fine fiber obtained by the fibrillation process or the micronization process by the manufacturing method described above is used as it is or diluted with water, and dispersed by an appropriate dispersion process to prepare the separator of this embodiment. Therefore, it can be used as a dispersion for papermaking or coating.
• the timing of mixing fine fibers other than regenerated cellulose fine fibers it may be mixed with regenerated cellulose raw material (cut yarn) in the beating process from the pulp or cut yarn stage and beaten, or the beating-treated raw material may be high pressure You may mix in the process of performing the refinement
• Any dilution method may be used for dilution after the dispersion for papermaking or coating, or after mixing the raw materials, but it is appropriately selected according to the contents of the mixed raw material components.
• a disper-type stirrer, various homomixers, various line mixers and the like can be mentioned, but the invention is not limited to these.
• the film forming method mainly by the papermaking method will be described.
• the paper making method can be carried out using not only a batch type paper machine but also all industrially available continuous paper machines.
• the composite sheet material of the present embodiment can be suitably produced by an inclined wire type paper machine, a long net type paper machine, and a round net type paper machine.
• use one or more machines for example, an inclined wire type paper machine is used for the base layer paper and a round net type paper machine is used for the upper layer paper machine). It is also effective in some cases.
• the papermaking multistage for example, by performing carried out papermaking with a basis weight of 5 g / m 2 in the first stage, the thus obtained wet the second stage of the paper of 5 g / m 2 on paper, total 10 g / m 2
• This is a technique for obtaining the composite sheet material of the present invention having a basis weight of.
• the composite sheet material of the present invention when the upper layer and the lower layer are formed from the same dispersion, the composite sheet material of the present invention is a single layer, but the first layer as the lower layer uses fine fibers using, for example, fibrillated fibers. It is also possible to form a wet paper layer and then make paper with the above-described dispersion in the second stage, and allow the lower wet paper to function as a filter to be described later.
• the thin film sheet of the present embodiment uses fine fibers, it is preferable to use a filter cloth or a plastic wire having a fine structure in which the fine fibers do not come out during paper making when forming a film by the paper making method.
• a filter cloth or plastic wire having such a fine structure basically, the solid content in the dispersion for papermaking stops as wet paper, that is, 90% by weight as the solid content yield in the papermaking process.
• industrially suitable production is possible by selecting a filter cloth or plastic wire that is preferably 95% by weight or more, more preferably 99% by weight or more.
• a high yield also means that the bite into the filter is low, which is preferable in that the peelability after papermaking becomes good.
• the filter mesh size is desirable to reduce because the yield is improved.
• the filterability is deteriorated, it is not preferable because the production rate of wet paper is reduced. That is, the water permeation amount of wire mesh or cloth under 25 ° C. atmospheric pressure, is preferably 0.005ml / cm 2 ⁇ s or more, more preferably 0.01ml / cm 2 ⁇ s or more, productivity From this point of view, it is possible to make a suitable paper.
• TETEXMONODW07-8435-SK010 manufactured by SEFAR (Switzerland)
• NT20 PET / nylon blend
• Shikishima Canvas Co examples thereof include, but are not limited to, plastic wire LTT-9FE manufactured by Nippon Filcon and multilayered wires described in JP2011-42903A.
• the wet paper having a solid content of 4% by weight or more of the cellulose fibers can be produced by depositing on the filter cloth by filtering by operating suction or the like.
• the solid content in this case is preferably as high as possible, preferably 8% by weight or more, and more preferably 12% by weight or more.
• the film is dried by a drying facility such as a drum dryer and wound up as a thin film sheet.
• the separator of the present invention can be obtained by drying the wet paper. Drying is usually performed under atmospheric pressure in a drum dryer or a pin tenter type hot air drying chamber, but depending on circumstances, drying under pressure or vacuum may be performed. At this time, it is more preferable to dry the wet paper with a drum dryer that can be effectively dried for a fixed length for the purpose of ensuring uniformity of physical properties and suppressing shrinkage in the width direction.
• the drying temperature may be appropriately selected within the range of 60 ° C to 150 ° C. In some cases, multi-stage drying such as rough drying at a low temperature of about 60 to 80 ° C. to give the wet paper self-supporting property and the main drying step at 100 ° C. or more may be effective in operation. is there.
• the thin film sheet of the present embodiment In order to continuously form the thin film sheet of the present embodiment, it is often effective to continuously perform the paper making process and the drying process as described above, and in some cases, the smoothing process by a calendar process.
• the smoothing process By performing the smoothing process with a calendar device, the above-described thin film can be formed, and the thin film sheet of the present invention having a wide range of combinations of film thickness / air resistance / strength can be provided.
• a super calendar device in addition to a normal calendar device using a single press roll, a super calendar device having a structure in which these are installed in a multistage manner may be used.
• the papermaking filter cloth or plastic wire to be used is an endless specification, and the entire process is performed with one wire, or the endless filter or endless of the next process is performed on the way.
• the felt cloth can be picked up and transferred or transferred, or the entire film forming process or a part of the film forming process can be made a roll-to-roll process using a filter cloth.
• the manufacturing method of the separator of this embodiment is not limited to this.
• the cellulose fine fiber layer containing 50% by weight or more of regenerated cellulose fine fibers is designed to have a specific surface area equivalent fiber diameter of 0.20 ⁇ m or more and 2.0 ⁇ m or less. Further, it is possible to prevent drying shrinkage derived from the cellulose hydroxyl group during sheet formation, and to maintain the porosity and the pore diameter. Since the pore diameter can be maintained, the cellulose fine fiber layer can be easily impregnated with the resin, and the cellulose fine fiber layer and the resin can be combined.
• thermosetting resins and photocurable resins examples include thermosetting resins and photocurable resins, resins obtained by thermosetting or photocuring these resins, and thermoplastic resins.
• thermosetting resins that can be impregnated into the regenerated cellulose fine fiber layer include epoxy resins, acrylic resins, oxetane resins, unsaturated polyester resins, alkyd resins, novolac resins, resole resins, urea resins. , Melamine resins and the like, and these can be used alone or in combination of two or more.
• thermosetting resins have excellent refractive index, improved curability, improved adhesion, improved flexibility of cured molded products, and improved handling properties due to lower viscosity of thermosetting resin compositions.
• a thermosetting compound suitable for each purpose it may be individual or a mixture of two or more.
• the addition amount of the thermosetting compound is preferably 10 to 1,000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the regenerated fine cellulose fiber layer.
• the addition amount is 10 parts by mass or more, it is effective for exhibiting thermal stability (reduction of linear thermal expansion coefficient, elasticity retention at high temperature), and when the addition amount is 1,000 parts by mass or less, thermosetting is performed. It is possible to maintain high permeability and high heat resistance of the conductive resin assembly and the cured molded product.
• An epoxy compound that can be added as a thermosetting resin is, for example, an epoxy compound containing an aromatic group that has thermal stability at high temperatures.
• examples include bifunctional or higher glycidyl ether type epoxy resins.
• a glycidyl ether type epoxy resin obtained by reaction of 1,6-dihydroxynaphthalene, 9,9-bis (4-hydroxyphenyl) fluorene, tris (p-hydroxyphenyl) methane, tetrakis (p-hydroxyphenyl) ethane and epichlorohydrin Can be mentioned.
• an epoxy resin having a dicyclopentadiene skeleton, an epoxy resin having a biphenylaralkyl skeleton, and triglycidyl isocyanurate can be given.
• an aliphatic epoxy resin and an alicyclic epoxy resin can also be mix
• a liquid aromatic diamine curing agent as a curing agent.
• the liquid state means a liquid at 25 ° C. and 0.1 MPa.
• the aromatic diamine curing agent means a compound having two amine nitrogen atoms directly bonded to an aromatic ring in the molecule and having a plurality of active hydrogens.
• active hydrogen refers to a hydrogen atom bonded to an aminic nitrogen atom.
• liquid aromatic diamine curing agents such as diamine and 4,6-diethyl-2-methyl-1,3-phenylenediamine. These liquid aromatic diamine curing agents may be used alone or in combination.
• a latent curing agent may be added as a thermosetting resin that can be added in addition to the epoxy compound.
• a latent curing agent is a compound that is insoluble in an epoxy resin at room temperature, solubilized by heating, and functions as a curing accelerator. It is an imidazole compound that is solid at room temperature, and a solid-dispersed amine adduct system latency.
• the curing accelerator include a reaction product of an amine compound and an epoxy compound (amine-epoxy adduct system), a reaction product of an amine compound and an isocyanate compound or a urea compound (urea type adduct system), and the like.
• Examples of the epoxy compound used as one of the raw materials for producing the solid dispersion type amine adduct-based latent curing accelerator include polyphenols such as bisphenol A, bisphenol F, catechol, and resorcinol, glycerin, Polyglycidyl ether obtained by reacting a polyhydric alcohol such as polyethylene glycol with epichlorohydrin; reacting a hydroxycarboxylic acid such as p-hydroxybenzoic acid or ⁇ -hydroxynaphthoic acid with epichlorohydrin Glycidyl ether ester obtained by reaction of polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin; epiglycidyl ester such as 4,4'-diaminodiphenylmethane and m-aminophenol A glycidylamine compound obtained by reacting with rhohydrin; a polyfunctional epoxy compound such as an phenol A, bisphenol F, catechol, and
• the amine compound used as another raw material for producing the solid dispersion-type amine adduct-based latent curing accelerator has at least one active hydrogen capable of undergoing addition reaction with an epoxy group in the molecule, and a primary amino group, What is necessary is just to have at least one functional group selected from the secondary amino group and the tertiary amino group in the molecule. Examples of such amine compounds are shown below, but are not limited thereto.
• aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane; 4,4'-diaminodiphenylmethane , Aromatic amine compounds such as 2-methylaniline; heterocyclic rings containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, piperazine Compound; and the like.
• a photoacid generator may be added as a resin that can be added in addition to the epoxy compound as the thermosetting resin of the present development.
• the photoacid generator one that generates an acid capable of cationic polymerization upon irradiation with ultraviolet rays is used.
• examples of such a photoacid generator include anions such as SbF 6 ⁇ , PF 6 ⁇ , BF 4 ⁇ , AsF 6 ⁇ , (C 6 F 5 ) 4 ⁇ , and PF 4 (CF 2 CF 3 ) 2 —.
• Examples include onium salts (diazonium salts, sulfonium salts, iodonium salts, selenium salts, pyridinium salts, ferrocenium salts, phosphonium salts, and the like) composed of a component and a cationic component. These may be used alone or in combination of two or more. Specifically, aromatic sulfonium salts, aromatic iodonium salts, aromatic phosphonium salts, aromatic sulfoxonium salts, and the like can be used. Among these, from the viewpoint of photocurability and transparency, a photoacid generator containing hexafluorophosphate or hexafluoroantimonate as an anionic component is preferable.
• the content of the photoacid generator needs to be set in the range of 0.5 to 2.0 parts by weight with respect to 100 parts by weight of the total weight of the epoxy compound. More preferably, it is in the range of 0.5 to 1.5 parts by weight. If the content of the photoacid generator is too small, the curability may be deteriorated or the heat resistance may be lowered. If the content is too large, the curability is improved while the transparency is impaired. .
• thermosetting resin of the present invention can be added in addition to the epoxy compound.
• a photosensitizer such as anthracene, an acid proliferating agent, or the like can be blended as necessary.
• coupling agents such as a silane type or a titanium type.
• an antioxidant, an antifoaming agent, etc. can be mix
• Examples of the photocurable resin that can be impregnated into the regenerated cellulose fine fiber layer include compounds having one or more (meth) acryloyl groups in one molecule.
• the photo-curing resin has excellent properties for improving the refractive index, improving the curability, improving the adhesion, improving the flexibility of the cured molded product, and improving the handling property by reducing the viscosity of the photosensitive resin composition.
• the amount of the compound having one or more (meth) acryloyl groups in one molecule is preferably 10 to 1,000 parts by mass with respect to 100 parts by weight of the regenerated fine cellulose fiber layer, More preferred is 500 parts by mass.
• the addition amount is 10 parts by mass or more, it is effective for exhibiting thermal stability (reduction of linear thermal expansion coefficient, elasticity retention at high temperature).
• the addition amount is 1,000 parts by mass or less, photosensitivity It is possible to maintain high permeability and high heat resistance of the resin assembly and the cured molded product.
• the (meth) acrylate compound that can be added as a photocurable resin is, for example, a (meth) acrylate compound containing an aromatic group having thermal stability at high temperatures.
• a (meth) acrylate compound containing an aromatic group having thermal stability at high temperatures examples include phenoxyethyl acrylate, paraphenylphenoxyethyl acrylate (Aronix TO-1463 manufactured by Toagosei Co., Ltd.), paraphenylphenyl acrylate (Aronix TO-2344 manufactured by Toagosei Co., Ltd.), phenylglycidyl ether acrylate (hereinafter “PGEA”).
• photopolymerization initiator is added to the photocurable resin for the purpose of imparting a photosensitive pattern.
• the photopolymerization initiator (C) include the following photopolymerization initiators (1) to (10): (1) Benzophenone derivatives: for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone, (2) Acetophenone derivatives: For example, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE651 manufactured by BASF) 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184 manufactured by BASF), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE 907 manufactured by BASF), 2-hydroxy-1
• ⁇ -hydroxy ketone compounds for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl ⁇ -2-methylpropane, (8) ⁇ -aminoalkylphenone compounds: for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE369 manufactured by BASF), 2-dimethylamino-2- ( 4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (IRGACURE 379 manufactured by BASF), (9) Phosphine oxide compounds: For example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
• the content of the photopolymerization initiator is preferably 0.01% by mass or more, more preferably 0.1% by mass from the viewpoint of obtaining sufficient sensitivity based on the mass of all components other than the solvent in the photosensitive resin composition. On the other hand, from the viewpoint of sufficiently curing the bottom portion of the photosensitive resin layer, it is preferably 15% by mass or less, and more preferably 10% by mass or less. If desired, a sensitizer for improving photosensitivity can be added to the photocurable resin.
• sensitizers include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylamino).
• a polymerization inhibitor can be added to the photosensitive resin composition for the purpose of improving the viscosity during storage and the stability of photosensitivity.
• examples of such polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid.
• the photosensitive resin composition includes various kinds of photosensitive resin compositions as necessary as long as they do not inhibit various characteristics of the photosensitive resin composition, including an ultraviolet absorber and a coating film smoothness imparting agent. Additives can be blended as appropriate.
• thermosetting resin or a photocurable resin can also be used, but a sheet-like substrate can be impregnated with the resin in a short time by injection molding, etc. It is preferable to use a thermoplastic resin from the viewpoint of providing it and easily adapting to various molded shapes.
• thermoplastic resin for example, polyolefin (polyethylene, polypropylene, etc.) like general-purpose plastics, ABS, polyamide, polyester, polyphenylene ether, polyacetal, polycarbonate, polyphenylene sulfide, polyimide, polyetherimide, Polyether sulfone, polyketone, polyether ether ketone, combinations thereof, and the like can be used.
• inorganic fine particles may be added to the resin impregnated into the regenerated cellulose fine fiber layer from the viewpoint of improving the thermal stability (linear thermal expansion coefficient and elasticity at high temperature) of the resin.
• the inorganic fine particles for example, those having excellent heat resistance include alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, amorphous fine powder amorphous Silica, etc.), etc .; those having excellent thermal conductivity, such as boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc .; those having excellent conductivity include simple metals or alloys (for example, , Iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel) and / or metal-coated fillers; mica, clay, kaolin, talc
• These inorganic fine particles may be appropriately selected depending on the application, and may be used alone or in combination of two or more. The inorganic fine particles have various characteristics other than the special products mentioned in the examples, and may be selected according to the timely use.
• silica when silica is used as the inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdered silica and colloidal silica can be used.
• known silica fine particles such as powdered silica and colloidal silica can be used.
• commercially available powdered silica fine particles include Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., and E220A manufactured by Nippon Silica Industry Co., Ltd. , E220, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.
• colloidal silica examples include methanol silica sol, IPA-ST, PGM-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, manufactured by Nissan Chemical Industries, Ltd. ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned.
• silica fine particles may be used.
• the silica fine particles may be surface-treated with a reactive silane coupling agent having a hydrophobic group or those modified with a compound having a (meth) acryloyl group.
• a reactive silane coupling agent having a hydrophobic group or those modified with a compound having a (meth) acryloyl group.
• silica powder modified with a compound having a (meth) acryloyl group as commercially available colloidal silica modified with a compound having a (meth) acryloyl group, such as Aerosil RM50, R7200, R711 manufactured by Nippon Aerosil Co., Ltd.
• a colloidal silica surface-treated with a reactive silane coupling agent having a hydrophobic group such as MIBK-SD, MEK-SD manufactured by Nissan Chemical Industries, Ltd., and MIBK-ST manufactured by Nissan Chemical Industries, Ltd. MEK-ST etc. are mentioned.
• the shape of the silica fine particles is not particularly limited, and those having a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape can be used.
• a commercially available hollow silica fine particle Sirenax manufactured by Nittetsu Mining Co., Ltd. can be used.
• the primary particle diameter of the inorganic fine particles is preferably in the range of 5 to 2,000 nm. When it is 5 nm or more, the inorganic fine particles in the dispersion are excellently dispersed, and when the diameter is within 2,000 nm, the strength of the cured product is good. More preferably, it is 10 nm to 1,000 nm.
• the “particle size” here is measured using a scanning electron microscope (TEM) or the like.
• the inorganic fine particles are preferably blended at a ratio of 5 to 50% by weight with respect to the total solid content of the resin composite.
• the silica fine particle is preferably 5 to 50% by weight in order to achieve both a low linear expansion coefficient and a high strength of the cured product, and 20 to 20% in order to further reduce the linear expansion coefficient. More preferably, it is added in a proportion of 50% by weight, more preferably 30 to 50% by weight.
• the viscosity can be adjusted by adding a solvent as necessary.
• suitable solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclohexane Pentanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, tetramethyl urea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone Methyl isobutyl ketone, anisole, ethyl acetate, ethy
• N-methyl-2-pyrrolidone, ⁇ -butyrolactone, and propylene glycol monomethyl ether acetate are particularly preferable.
• These solvents can be appropriately added at the time of resin impregnation into the regenerated cellulose fine fiber layer depending on the coating film thickness and viscosity.
• the production method for impregnating the regenerated cellulose fine fiber layer with resin is not particularly limited, but after shaping and / or laminating a prepreg impregnated with a thermosetting resin composition in a thin film sheet, Alternatively, a prepreg laminate molding method in which a resin is heated and cured while applying pressure to the laminate, a resin transfer molding method in which a thin film sheet is directly impregnated with a liquid thermosetting resin composition and then cured, and a thin film sheet is liquid thermoset A pultrusion method in which the resin composition is continuously passed through an impregnation tank filled with the resin composition and impregnated with the thermosetting resin composition, and then molded and cured while being continuously pulled out by a pulling machine through a squeeze die and a heating mold. Can be manufactured.
• Examples of the method for impregnating the resin include a wet method and a hot melt method (dry method).
• a wet method after immersing the thin film sheet in a solution in which an epoxy resin composition, a photocurable resin composition, or a thermoplastic resin is dissolved in a solvent such as methyl ethyl ketone, the thin film sheet is pulled up and the solvent is evaporated using an oven or the like.
• Hot melt methods include epoxy resin compositions and photo-curing resin compositions whose viscosity has been reduced by heating, a method of impregnating a thermoplastic resin directly into a thin film sheet, a film coated with an epoxy resin composition on release paper, etc.
• the content of the cellulose fine fiber layer in the prepreg or its cured resin or thermoplastic resin is preferably 1 to 80% by weight, more preferably 5 to 50% by weight, still more preferably 10 to 30% by weight. is there.
• the weight content of the cellulose fine fiber layer is less than 1% by weight, the ratio of the resin is too high, so that it is difficult to obtain the advantage of the composite material having excellent linear thermal expansion coefficient and elastic modulus when combined.
• the mass content of the reinforcing fibers exceeds 80% by weight, the amount of impregnation of the resin is insufficient, so that the obtained composite material has many voids, and the strength necessary for the sheet is also lowered.
• the thin film sheet of this embodiment is a fiber reinforced plastic core material, more specifically, a printed wiring board core material for electronic materials, an insulating film core material, a core material core material, or an electronic material It can be suitably used as a printed circuit board prepreg, an insulating film prepreg, and a core material prepreg, and further as a printed wiring board, insulating film, and core material. Furthermore, it can also be used in a wide range of fields such as substrates for semiconductor devices, flexible base materials of low linear expansion coefficient materials, and the like.
• the thin film sheet of the present invention can be used very suitably from the viewpoints of device compactness and weight reduction.
• it can be a core material for a fiber-reinforced plastic film that is thin and excellent in suitability even in processing steps such as resin impregnation.
• the thin film sheet of this embodiment becomes high intensity
• Examples include industrial machine parts (eg, electromagnetic equipment casings, roll materials, transfer arms, medical equipment members, etc.), general machine parts, automobile / railway / vehicle parts (eg, outer plates, chassis, aerodynamics). Members, seats, etc.), ship components (eg, hulls, seats, etc.), aircraft-related parts (eg, fuselage, main wing, tail wing, moving wing, fairing, cowl, door, seat, interior materials, etc.), spacecraft, artificial satellite Member (motor case, main wing, structure, antenna, etc.), electronic / electrical parts (eg personal computer housing, mobile phone housing, OA equipment, AV equipment, telephone, facsimile, household appliances, toy supplies, etc.), construction / civil engineering Materials (for example, rebar replacement materials, truss structures, cables for suspension bridges, etc.), household items, sports / leisure items (for example, golf club shafts, fishing rods, teni And like racket badminton), a wind power generation housing member or the like, also containers
• the thin film sheet of this embodiment can be suitably used as a separator for an electricity storage device.
• the thin film sheet is essentially any primary battery, secondary battery (for example, lithium secondary ion battery), electrolytic capacitor (aluminum electrolytic capacitor), electric double layer capacitor, or separator as a power storage device separator. It can be applied to new electricity storage devices required as a device (for example, devices described in Japanese Patent Application Laid-Open No. 2004-079321). It can be applied in almost all the styles used.
• the performance of the separator for an electricity storage device is suitably exhibited particularly in an electric double layer capacitor, a liquid type or solid type aluminum electrolytic capacitor, a lithium ion secondary battery, or a lithium ion capacitor. The reason is as follows.
• a general electricity storage device in an electric double layer capacitor, has a structure of electrode / electrolyte / separator / electrolyte / electrode, whereas the portion of the electrolyte in the structure is several ⁇ m to several tens ⁇ m.
• the activated carbon layer impregnated with the particle-based electrolytic solution is replaced with a structure. Since the activated carbon layer substantially functions as an electrode, the electrode layer is close to the middle of the separator, and the electrode has a fine particle laminated structure, so that it is easy to cause a so-called short circuit through the separator.
• the electric double layer capacitor needs to completely remove moisture in the activated carbon which is very hygroscopic in the manufacturing process.
• the assembly process of the electric double layer is to remove the moisture after making a laminated structure other than the electrolyte, and finally inject the electrolyte. Therefore, in the drying process for removing moisture, the activated carbon layer including the separator Will be exposed to high temperatures.
• drying in order to completely remove water in the activated carbon, drying is often performed under conditions of 150 ° C. or higher. That is, the separator is required to have heat resistance enough to withstand this condition.
• the separator for an electricity storage device since the separator for an electricity storage device has particularly excellent performance in terms of short-circuit resistance and heat resistance, it functions suitably particularly in an electric double layer capacitor. Furthermore, the separator of the present invention works extremely well in other power storage devices such as a lithium secondary ion battery using an organic electrolytic solution, as well as an electric double layer capacitor.
• the fiber diameter corresponding to the specific surface area of the fibers constituting the cellulose fine fiber layer is 0.20 ⁇ m or more and 0.45 ⁇ m or less, and the air resistance is particularly dependent on the type of device.
• the degree is in the range of 5 s / 100 ml or more and 40 s / 100 ml or less, it can be suitably used from the viewpoint of short circuit resistance. However, it is not limited to this condition.
• the electricity storage device such as an electric double layer capacitor using the electricity storage device separator of the present embodiment, the following effects can be expected.
• the separator thickness can be reduced to 22 ⁇ m or less while satisfying the basic conditions for a separator, such as short-circuit resistance, and the porosity in the separator can also be set high, so compared with the case where a conventional separator is used.
• the internal resistance can be reduced.
• the productivity is also improved.
• the separator itself may be required to have higher heat resistance than that used for consumer use, and therefore the high heat resistance of the separator of this embodiment contributes effectively. To do.
• other power storage devices also contribute to lower internal resistance.
• Example 1 Put the tencel cut yarn (3mm length), a regenerated cellulose fiber obtained from Sojitz Corporation, into the washing net, add a surfactant, and wash it with water many times in the washing machine to remove the oil on the fiber surface. did.
• the obtained refined tencel fiber (cut yarn) was dispersed in water to a solid content of 1.5% by weight (400 L), and SDR14 type laboratory refiner (pressure type DISK) manufactured by Aikawa Tekko Co., Ltd. was used as a disc refiner device.
• aqueous dispersion 400 L of the aqueous dispersion was beaten for 20 minutes with a disc clearance of 1 mm. Subsequently, thorough beating was performed under conditions where the clearance was reduced to almost zero, and a beating water dispersion (solid content concentration: 1.5% by weight) was obtained.
• the obtained beating water dispersion was subjected to refinement treatment 5 times under an operating pressure of 100 MPa using a high-pressure homogenizer (NS015H manufactured by Niro Soabi (Italy)) as it was, and an aqueous dispersion M1 of fine cellulose fibers ( Solid content concentration: 1.5% by weight).
• the water dispersion M1 was diluted to a solid content concentration of 0.1% by weight and dispersed with a blender, and then a plain fabric made of PET / nylon blend (NT20, manufactured by Shikishima Canvas Co., Ltd.) Permeation amount: 0.03ml / cm 2 ⁇ s, batch type paper machine (made by Kumagai Riki Kogyo Co., Ltd., automatic angle) set with fine cellulose fibers and capable of filtering 99% or more by filtration at 25 ° C under atmospheric pressure Using the fine cellulose sheet having a basis weight of 10 g / m 2 on a mold sheet machine (25 cm ⁇ 25 cm, 80 mesh) as a guide, the adjusted papermaking slurry was added, and then papermaking (dehydration) was performed at a reduced pressure of 4 KPa with respect to atmospheric pressure.
• the wet paper made of the concentrated composition in a wet state on the obtained filter cloth is peeled off from the wire and pressed at a pressure of 1 kg / cm 2 for 1 minute, and then the wet paper surface is brought into contact with the drum surface.
• the wet paper is dried for about 120 seconds with the drum dryer having a surface temperature set to 130 ° C. so that the wet paper is in contact with the drum surface.
• the filter cloth was peeled off from the cellulose sheet-like structure to obtain a sheet (25 cm ⁇ 25 cm) composed of white uniform cellulose fine fibers.
• the obtained fine cellulose sheet was produced with white fine cellulose shown in Table 1 below by performing a hot press treatment at 150 ° C. ⁇ 1.55 t / 20 cm by a calender machine (manufactured by Yuri Roll Co., Ltd.).
• a thin film sheet S1 was obtained.
• Example 2 The same operation as in Example 1 was carried out except that the papermaking slurry prepared by diluting M1 of Example 1 with water was adjusted so as to be a fine cellulose sheet having a basis weight of 5 g / m 2. Thus, a thin film sheet S2 made of white fine cellulose shown in Table 1 below was obtained.
• Example 3 The beating water dispersion (solid content concentration: 1.5% by weight) obtained in Example 1 was treated 10 times as it was using a high-pressure homogenizer (NS015H manufactured by Niro Soabi (Italy)) under an operating pressure of 100 MPa.
• the thin film sheet S3 produced with the white fine cellulose shown in the following Table 1 was obtained by operating like Example 1 except that.
• Example 4 The beating water dispersion obtained in Example 1 (solid content concentration: 1.5% by weight) was directly treated 30 times using a high pressure homogenizer (NS015H manufactured by Niro Soabi (Italy)) under an operating pressure of 100 MPa.
• the thin film sheet S4 produced with the white fine cellulose shown in the following Table 1 was obtained by operating like Example 1 except that.
• Example 5 To the papermaking slurry prepared by diluting M1 of Example 1 with water, Meikanate WEB (manufactured by Meisei Chemical Co., Ltd.) was added in an amount of 5% by weight of the cellulose fine fiber weight, and a fine cellulose sheet having a total basis weight of 11 g / m 2 A thin film sheet S5 made of white fine cellulose shown in Table 1 below was obtained by performing the same operation as in Example 1 except that the papermaking slurry thus adjusted was added.
• Meikanate WEB manufactured by Meisei Chemical Co., Ltd.
• Example 6 A thin film sheet made of the white fine cellulose shown in Table 1 below by operating in the same manner as in Example 1 except that Bemberg, a regenerated cellulose fiber obtained from Asahi Kasei Fibers Co., Ltd., was used as a raw material. S6 was obtained.
• Example 7 Linter pulp, which is natural cellulose as a raw material, is immersed in water to 4% by weight, heat-treated in an autoclave at 130 ° C. for 4 hours, and the resulting swollen pulp is washed with water many times and impregnated with water. A swollen pulp in a finished state was obtained. This was thoroughly beaten in the same manner as in Example 1, and subsequently subjected to refinement five times at an operating pressure of 100 MPa using a high-pressure homogenizer to obtain an aqueous dispersion M2 having a solid content concentration of 1.5 wt%. It was.
• a thin film sheet S7 made of white fine cellulose shown in Table 1 below was obtained by the same operation as in Example 1 except that 5% by weight of the weight of cellulose fine fiber was added.
• Meikanate WEB manufactured by Meisei Chemical Co., Ltd.
• Example 9 Abaca pulp, which is natural cellulose as a raw material, is immersed in water so as to be 4% by weight, heat-treated in an autoclave at 130 ° C. for 4 hours, and the obtained swollen pulp is washed with water many times and impregnated with water. A swollen pulp in a state was obtained. This was thoroughly beaten in the same manner as in Example 1, and subsequently subjected to refinement five times at an operating pressure of 100 MPa using a high-pressure homogenizer to obtain an aqueous dispersion M2 having a solid content concentration of 1.5 wt%. It was.
• Example 10-1 Aramid pulp, which is an organic polymer as a raw material, was put into a washing net, a surfactant was added, and the oil agent on the fiber surface was removed by washing with a washing machine many times.
• the obtained refined tencel fiber (cut yarn) was dispersed in water to a solid content of 1.5% by weight (400 L), and SDR14 type laboratory refiner (pressure type DISK) manufactured by Aikawa Tekko Co., Ltd. was used as a disc refiner device.
• 400 L of the aqueous dispersion was beaten for 20 minutes with a disc clearance of 1 mm.
• beating water dispersion solid content concentration: 1.5% by weight
• the obtained beating water dispersion was subjected to a fine treatment under an operating pressure of 100 MPa using a high-pressure homogenizer (NS015H manufactured by Niro Soabi (Italy)) as it was, and an aqueous dispersion M4 of aramid nanofibers (solid content concentration) : 1.5% by weight).
• Example 10-2 Aramid pulp, which is an organic polymer as a raw material, was put into a washing net, a surfactant was added, and the oil agent on the fiber surface was removed by washing with a washing machine many times.
• the obtained refined tencel fiber (cut yarn) was dispersed in water to a solid content of 1.5% by weight (400 L), and SDR14 type laboratory refiner (pressure type DISK) manufactured by Aikawa Tekko Co., Ltd. was used as a disc refiner device.
• SDR14 type laboratory refiner pressure type DISK
• 400 L of the aqueous dispersion was beaten for 20 minutes with a disc clearance of 1 mm. Subsequently, thorough beating was performed under conditions where the clearance was reduced to almost zero, and a beating water dispersion (solid content concentration: 1.5% by weight) was obtained.
• the obtained beating water dispersion was subjected to a fine treatment under an operating pressure of 100 MPa using a high-pressure homogenizer (NS015H manufactured by Niro Soabi (Italy)) as it was, and an aqueous dispersion M4 of aramid nanofibers (solid content concentration) : 1.5% by weight).
• a high-pressure homogenizer N015H manufactured by Niro Soabi (Italy)
• WEB Wired Equivalent Bond
• a thin film sheet S10-2 made of white fine cellulose as shown in Table 1 below was obtained by performing the same operation as in Example 1 except that 5% by weight of Chemical Fiber) was added. .
• Example 11 A polyacrylonitrile fiber, which is an organic polymer as a raw material, was put into a washing net, a surfactant was added, and the oil agent on the fiber surface was removed by washing with a washing machine many times.
• the obtained refined tencel fiber (cut yarn) was dispersed in water to a solid content of 1.5% by weight (400 L), and SDR14 type laboratory refiner (pressure type DISK) manufactured by Aikawa Tekko Co., Ltd. was used as a disc refiner device. Using a formula, 400 L of the aqueous dispersion was beaten for 20 minutes with a disc clearance of 1 mm.
• beating water dispersion solid content concentration: 1.5% by weight
• the obtained beating water dispersion was subjected to a micronization treatment under an operating pressure of 100 MPa using a high-pressure homogenizer (NS015H manufactured by Niro Soabi (Italy)) as it was, and an aqueous dispersion M5 of polyacrylonitrile nanofibers (solid content) Concentration: 1.5% by weight).
• Example 12 To M1 papermaking slurry prepared by diluting with water in Example 1, Meikaneto the WEB (manufactured by Meisei Chemical Co., Ltd.) was added 5 wt% of the cellulose fine fiber weight, and the total basis weight 5 g / m 2 of fine cellulose sheet Table 1 below shows the same procedure as in Example 1 except that the papermaking slurry thus prepared was put on a cellulose continuous fiber nonwoven fabric having a basis weight of 14 g / m 2 obtained from Asahi Kasei Fibers Co., Ltd. A thin film sheet S12 made of the white fine cellulose shown was obtained.
• Example 13 A commercially available epoxy thermosetting resin aqueous dispersion (solid content concentration 20% by weight), ⁇ -alumina powder (average particle size: 0.9 ⁇ m), and distilled water were prepared, and the composition was determined based on the epoxy thermosetting resin.
• Example 14 After the thin film sheet S1 produced in Example 1 was treated by the gravure roll method in the same manner as in Example 13 except that the epoxy thermosetting resin / ⁇ -alumina basis weight was 3 g / m 2. Further, on the back side, the above coating liquid was treated in the same manner as in Example 13 except that the epoxy-based thermosetting resin / ⁇ -alumina basis weight was 3 g / m 2 by the gravure roll method. A thin film sheet S14 made of white fine cellulose shown in Table 1 below was obtained, in which 3 g / m 2 each of epoxy thermosetting resin / ⁇ -alumina basis weight was laminated.
• Example 1 The same operation as in Example 1 was conducted except that the papermaking slurry prepared by diluting M1 of Example 1 with water was added to the papermaking slurry adjusted to be a fine cellulose sheet having a basis weight of 30 g / m 2. Thus, a reference sheet R1 shown in Table 1 below was obtained.
• Example 2 The same operation as in Example 1 was carried out except that the papermaking slurry prepared by diluting M1 of Example 1 with water was adjusted so as to obtain a fine cellulose sheet having a basis weight of 3 g / m 2. Thus, a reference sheet R2 shown in Table 1 below was obtained.
• Specific surface area equivalent fiber diameter measurement After measuring the adsorption amount of nitrogen gas at the boiling point of liquid nitrogen to about 0.2 g of a thin film sheet sample with a specific surface area / pore distribution measuring device (manufactured by Beckman Coulter, Inc.), The specific surface area (m 2 / g) is calculated by the same apparatus program, and is a cylinder model assuming that the cellulose density is 1.50 g / ml in an ideal state in which no fusion between fibers occurs (a cylinder having a circular cross section.
• a composite prepreg sheet was produced by impregnating the thin film sheet S1 with a resin component.
• a 10 cm square thin film sheet and a 50 ⁇ m thick spacer were placed on a PET film coated with a release agent.
• a liquid mixture prepared in advance with the composition shown in Table 2 which was stirred and mixed was dropped onto the thin film sheet, and a PET film coated with a release agent was placed thereon.
• a composite prepreg in which white fine cellulose described in Table 2 below is impregnated with an epoxy resin by pressing this sheet from the top of the PET film at 10 kg / cm 2 , vacuum defoaming, and standing at room temperature for several days. Sheets C1, C2, and C3 were obtained.
• Example 15 C1 Epoxy resin: Epoxy resin JER828 (Mitsubishi Chemical Corporation) Curing agent: ST12 (Mitsubishi Chemical Corporation)
• Example 16 C2 Epoxy resin: Epoxy resin JER825 (Mitsubishi Chemical Corporation) Curing Agent: Latent Curing Agent Fuji Cure FXE1000 (Fuji Kasei Co., Ltd.) Inorganic fine particles: Colloidal silica (manufactured by Nissan Chemical Co., Ltd.)
• a composite sheet was prepared by impregnating a thin film sheet with a resin component.
• a 10 cm square thin film sheet and a spacer having a predetermined thickness were placed on a PET film coated with a release agent.
• the composition described in Table 2 that had been stirred and mixed in advance and the thin film sheet were combined, and a PET film coated with a release agent was placed thereon. This sheet was vacuum degassed while being pressed from above the PET film at 10 kg / cm 2 .
• Example 18 C4 Epoxy resin: Epoxy resin JER828 (Mitsubishi Chemical Corporation) Curing agent: ST12 (Mitsubishi Chemical Corporation)
• Example 19 C5 Epoxy resin: Epoxy resin JER828 (Mitsubishi Chemical Corporation) Curing agent: ST12 (Mitsubishi Chemical Corporation)
• Example 20 C6 Epoxy resin: Epoxy resin JER825 (Mitsubishi Chemical Corporation) Curing Agent: Latent Curing Agent Fuji Cure FXE1000 (Fuji Kasei Co., Ltd.) Inorganic fine particles: Zirconia (Nissan Chemical)
• Example 21: C7 Acrylic resin: Ethoxylated bisphenol A dimethacrylate “BPE500” (manufactured by Shin-Nakamura Chemical Co., Ltd.) / Cyclomer P 230AA (manufactured by Daicel-Cytec) 60/40 Initiator: Irgacure 819
• Example 22 C8 Therm
• Composition Table 2 summarizes and describes the raw materials and content ratios used in the production of composite prepreg sheets in Examples 15 to 17.
• Composition Table 2 summarizes and describes the raw materials and content ratios used for producing composite sheets in Examples 18 to 29 and Comparative Examples 5 to 8.
• Measurement of sample thickness Using a Mitutoyo film thickness meter (Model ID-C112XB), a 10 cm ⁇ 10 cm square piece was cut out from the composite sheet, and the average value of five measured values at various positions was determined as the film thickness d. ( ⁇ m).
• ⁇ marks are marked with X marks for those showing an elastic modulus improvement effect of less than 1.2 times.
• Example 30 An electric double layer capacitor using the thin film sheet S1 as a separator was produced.
• the obtained slurry was coated on a current collector foil (Al foil with an anchor) with a coating apparatus (applicator), and dried on a hot plate at 120 ° C. for 10 minutes. After drying, an electrode having a thickness of 83 ⁇ m and an electric conductivity of 2.5 ⁇ 10 ⁇ 2 S / cm was produced using a calendar machine.
• the separator was S1 (drying condition: 150 ° C. ⁇ 12 hr), and the electrolyte was 1,4M-TEMA ⁇ BF4 /
• a single-layer laminate cell DC1 (aluminum laminate exterior) was prepared as PC.
• Examples 31 to 36, Comparative Examples 9 to 12 Using the compositions shown in Table 3 below, single-layer laminate cells DC2 to DC7 and reference cells DCR1 to DCR4 were obtained in the same manner as in Example 30.
• an electrode material, a conductive agent, a binder and N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) were added and kneaded to obtain a slurry.
• the obtained slurry was coated on a current collector foil (Al foil, Cu foil) with a coating apparatus (applicator), and dried on a hot plate at 120 ° C. for 10 minutes.
• positive electrode material 77 ⁇ m thickness, electric conductivity 2.1 ⁇ 10 ⁇ 2 S / cm, negative electrode material: 83 ⁇ m thickness, electric conductivity 2.0 ⁇ 10 ⁇ 1 were prepared with a calender.
• the separator was S1 (drying condition: 150 ° C. ⁇ 12 hr), and the electrolyte was 1M-LiPF6 (3EC / 7MEC), a single-layer laminate cell LD1 (aluminum laminate exterior) was produced.
• Example 38 to 43 Comparative Examples 13 to 16
• Table 4 single-layer laminate cells LD2 to LD7 and reference cells LDR1 to LDR4 were obtained in the same manner as in Example 35.
• the composite prepreg sheets of Examples 15 to 17 and the composite sheets of Examples 18 to 29 produced by combining the thin film sheets obtained in Examples 1 to 14 with each resin have a specific surface area equivalent fiber diameter.
• a regenerated cellulose of 0.20 ⁇ m or more and 2.0 ⁇ m or less a thin film sheet having a large pore diameter and a high porosity can be designed, so that the resin impregnation property to the thin film sheet is high and the composite is easy.
• nanofibers transparency when composited with resin and improvement of thermal stability of resin, especially compared with Comparative Example 5 or 6, reduction of linear thermal expansion coefficient and improvement of elastic modulus The effect was expressed.
• a thin film sheet containing aramid nanofibers has a higher porosity and is easily impregnated with resin, and at the same time, a thermal stability tends to be improved when a composite sheet is formed.
• the reference sheet obtained in Comparative Examples 1 to 4 and the composite sheets of Comparative Examples 7 and 8 prepared by combining each resin have a specific surface area equivalent fiber diameter of 0.1 ⁇ m. Therefore, it was found that the linear thermal expansion coefficient could not be reduced due to the fact that the resin was difficult to be impregnated even when composited, and the specific surface area equivalent diameter was 10 ⁇ m, so that even when composited, the number of entanglement points of cellulose fibers was small. .
• the thin film sheet of the present invention is thin and excellent in uniformity, and has a limited air permeability resistance range, that is, a pore diameter. Therefore, for example, when used as a substrate for fiber-reinforced plastic, thermal stability (reduction of linear thermal expansion coefficient and elastic retention at high temperature) at the time of compounding with a resin can be imparted. Moreover, when it uses as a base material for insulating films for electronic materials, sheet strength ensuring and thermal stability can be made compatible with a thin film. Furthermore, when used as a separator for an electricity storage device, it is a thin film and has excellent short-circuit resistance, heat resistance, and chemical / physical stability. Internal resistance, small leakage current value, etc.) and long-term stability can be realized. Therefore, the thin film sheet of the present invention can be suitably used in these technical fields.

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• 2015
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